Sample records for supercritical fluid selected

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercriticalfluid solvent containing a chelating agent. The chelating agent forms chelates that are soluble in the supercriticalfluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated or lipophilic crown ether or fluorinated dithiocarbamate. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The chelate and supercriticalfluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

In stationary phase optimized selectivity liquid chromatography (SOS-LC) the stationary phase becomes a tunable parameter by connecting column segments with variable lengths of different stationary phases. An optimization procedure and algorithm based on the PRISMA model for optimization of the mobile phase in LC was developed to apply this strategy for isocratic and gradient separations. An optimized column segment combination, giving the highest separation selectivity for all compounds in a...

A wide range of supercriticalfluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide–acetonitrile and supercritical HFCs. PMID:26574527

A wide range of supercriticalfluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide-acetonitrile and supercritical HFCs.

This report is made up of three independent papers: (1) SupercriticalFluid Extraction of Thorium and Uranium with Fluorinated Beta-Diketones and Tributyl Phosphate, (2) SupercriticalFluid Extraction of Lanthanides with Beta-Diketones and Mixed Ligands, and (3) A Group Contribution Method for Predicting the Solubility of Solid Organic Compounds in Supercritical Carbon Dioxide. Experimental data are presented demonstrating the successful extraction of thorium and uranium using fluorinated beta-diketones to form stable complexes that are extracted with supercritical carbon dioxide. The conditions for extracting the lanthanide ions from liquid and solid materials using supercritical carbon dioxide are presented. In addition, the Peng-Robison equation of state and thermodynamic equilibrium are used to predict the solubilities of organic solids in supercritical carbon dioxide from the sublimation pressure, critical properties, and a centric factor of the solid of interest.

Exciting opportunities exist for the application of supercriticalfluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we developed a method to tailor chemical reactions in supercriticalfluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as one model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane. The Diels-Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) was selected as a second model system, and it was investigated in supercritical carbon dioxide.

Full Text Available One of the most interesting areas of supercriticalfluids applications is the processing of novel materials. These new materials are designed to meet specific requirements and to make possible new applications in Pharmaceuticals design, heterogeneous catalysis, micro- and nano-particles with unique structures, special insulating materials, super capacitors and other special technical materials. Two distinct possibilities to apply supercriticalfluids in processing of materials: synthesis of materials in supercriticalfluid environment and/or further processing of already obtained materials with the help of supercriticalfluids. By adjusting synthesis parameters the properties of supercriticalfluids can be significantly altered which further results in the materials with different structures. Unique materials can be also obtained by conducting synthesis in quite specific environments like reversed micelles. This paper is mainly devoted to processing of previously synthesized materials which are further processed using supercriticalfluids. Several new methods have been developed to produce micro- and nano-particles with the use of supercriticalfluids. The following methods: rapid expansion of supercritical solutions (RESS supercritical anti-solvent (SAS, materials synthesis under supercritical conditions and encapsulation and coating using supercriticalfluids were recently developed.

Full Text Available The extension of the saturation curve ( on the PT diagram in the supercritical region for a number of monocomponent supercriticalfluids by peak values for different thermophysical properties, such as heat capacities and and compressibility has been studied. These peaks signal about some sort of fluid structural transition in the supercritical region. Different methods give similar but progressively diverging curves st( for this transition. The zone of temperatures and pressures near these curves can be named as the zone of the fluid structural transition. The outstanding properties of supercriticalfluids in this zone help to understand the physical sense of the fluid structural transition.

The effects of supercriticalfluids on the production of renewable diesel-range hydrocarbons from natural triglycerides were investigated. Various supercriticalfluids, which included CO2 (scCO2 ), propane (scC3 H8 ) and n-hexane (scC6 H14 ), were introduced with H2 and soybean oil into a fixed-bed reactor that contained pre-activated CoMo/γ-Al2 O3 . Among these supercriticalfluids, scC3 H8 and scC6 H14 efficiently allowed the reduction of the reaction temperature by as much as 50 °C as a result of facilitated heat and mass transfer and afforded similar yields to reactions in the absence of supercriticalfluids. The compositional analyses of the gas and liquid products indicated that the addition of scC3 H8 during the hydrotreatment of soybean oil promoted specific deoxygenation pathways, decarbonylation and decarboxylation, which consumed less H2 than the hydrodeoxygenation pathway. As a result, the quantity of H2 required to obtain a high yield of diesel-range hydrocarbons could be reduced to 57 % if scC3 H8 was used. As decarboxylation and decarbonylation are mildly endothermic reactions, the reduced heat transfer resistance in scC3 H8 may drive the deoxygenation reaction to thermodynamically favourable pathways.

Integrated studies were carried out in the areas of corrosion, thermodynamic modeling, and electrochemistry under pressure and temperature conditions appropriate for potential applications of supercriticalfluid (SCF) extractive metallurgy. Carbon dioxide and water were the primary fluids studied. Modifiers were used in some tests; these consisted of 1 wt% water and 10 wt% methanol for carbon dioxide and of sulfuric acid, sodium sulfate, ammonium sulfate, and ammonium nitrate at concentrations ranging from 0.00517 to 0.010 M for the aqueous fluids. The materials studied were Types 304 and 316 (UNS S30400 and S31600) stainless steel, iron, and AISI-SAE 1080 (UNS G10800) carbon steel. The thermodynamic modeling consisted of development of a personal computer-based program for generating Pourbaix diagrams at supercritical conditions in aqueous systems. As part of the model, a general method for extrapolating entropies and related thermodynamic properties from ambient to SCF conditions was developed. The experimental work was used as a tool to evaluate the predictions of the model for these systems. The model predicted a general loss of passivation in iron-based alloys at SCF conditions that was consistent with experimentally measured corrosion rates and open circuit potentials. For carbon-dioxide-based SCFs, measured corrosion rates were low, indicating that carbon steel would be suitable for use with unmodified carbon dioxide, while Type 304 stainless steel would be suitable for use with water or methanol as modifiers.

Full Text Available This paper reviews the current trends in the combined use of supported catalytic systems, either on solid supports or in liquid phases and supercriticalfluids (scFs, to develop selective and enantioselective chemical transformations under continuous and semi-continuous flow conditions. The results presented have been selected to highlight how the combined use of those two elements can contribute to: (i Significant improvements in productivity as a result of the enhanced diffusion of substrates and reagents through the interfaces favored by the scF phase; (ii the long term stability of the catalytic systems, which also contributes to the improvement of the final productivity, as the use of an appropriate immobilization strategy facilitates catalyst isolation and reuse; (iii the development of highly efficient selective or, when applicable, enantioselective chemical transformations. Although the examples reported in the literature and considered in this review are currently confined to a limited number of fields, a significant development in this area can be envisaged for the near future due to the clear advantages of these systems over the conventional ones.

A selective separation and recovery process has been developed based on the supercriticalfluid extraction and fractionation (SFEF) technology. The solvent used varies from C3 to C5, depending on process objective. Basic research work has been done on the phase behavior, phase equilibria and modeling of a number of systems including petroleum residue, polymers, waxes and lubricants with the light hydrocarbon solvents. Semi-batch pilot and continuous pilot experiments were performed to establish data base for the process design of industrial scale. The effects of operation para-meters, such as temperature, pressure, ratio of solvent to oil and residence time, on separation selectivity and yield of extracts were studied in a wide range. Industrial demonstration plant with a capacity of 15 kt/a was setup and has run for a sufficient long period of time to confirm the design and to obtain the energy cost and economic analysis data for further commercial scale up. It was found that the process offers high efficient products and solvent recovery.

This book presents the state-of-the-art in the science and technology of supercriticalfluid (scf) processing. Current research as described in the book, focuses on developments in equations of state for binary and multicomponent mixtures (including polymer solutions), solubility measurements at near-critical conditions, measurements of critical properties of binary mixtures and their correlation with equations of state. Progress in thermodynamics, coupled with advances in the design and construction of high pressure equipment, has opened up a wide avenue of commercial application (e.g. decaffeination of coffee beans, extractions of flavours and spices, purification of pharmaceutical products, separations of polymeric materials, deodorization and deacidification of vegetable oils, fractionation of fatty acids, coal liquefaction, wood delignitication, etc.)

A system and method for reactively refining hydrocarbons, such as heavy oils with API gravities of less than 20 degrees and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure, using a selectedfluid at supercritical conditions. A reaction portion of the system and method delivers lightweight, volatile hydrocarbons to an associated contacting unit which operates in mixed subcritical/supercritical or supercritical modes. Using thermal diffusion, multiphase contact, or a momentum generating pressure gradient, the contacting unit separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques.

Several techniques have been proposed to produce nanomaterials using ... of the supercritical based techniques applied to the production of nanoparticles materials. Keywords: Supercriticalfluids; Nanoparticles; SCF technology; RESS; SAS.

A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W.sub.o that determines the maximum size of the reverse micelles. The maximum ratio W.sub.o of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions.

A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

Full Text Available This review enlightens the role of supercriticalfluid chromatography (SFC in the field of lipid analysis. SFC has been popular in the late 1980s and 1990s before almost disappearing due to the commercial success of liquid chromatography (LC. It is only 20 years later that a regain of interest appeared when new commercial instruments were introduced. As SFC is fully compatible with the injection of extracts in pure organic solvent, this technique is perfectly suitable for lipid analysis and can be coupled with either highly universal (UV or evaporative light scattering or highly specific (mass spectrometry detection methods. A short history of the use of supercriticalfluids as mobile phase for the separation oflipids will be introduced first. Then, the advantages and drawbacks of SFC are discussed for each class of lipids (fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, sterols, prenols, polyketides defined by the LIPID MAPS consortium.

This review enlightens the role of supercriticalfluid chromatography (SFC) in the field of lipid analysis. SFC has been popular in the late 1980s and 1990s before almost disappearing due to the commercial success of liquid chromatography (LC). It is only 20 years later that a regain of interest appeared when new commercial instruments were introduced. As SFC is fully compatible with the injection of extracts in pure organic solvent, this technique is perfectly suitable for lipid analysis and can be coupled with either highly universal (UV or evaporative light scattering) or highly specific (mass spectrometry) detection methods. A short history of the use of supercriticalfluids as mobile phase for the separation oflipids will be introduced first. Then, the advantages and drawbacks of SFC are discussed for each class of lipids (fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, sterols, prenols, polyketides) defined by the LIPID MAPS consortium. PMID:26090714

In this review we examine the related fields of supercriticalfluid chromatography (SFC) and supercriticalfluid extraction (SFE). We reviewed the published literature in the period from November 2003 to November 2005. Well over 300 papers were published in this period. This large body of work indicates continuing active growth of the field, but an exhaustive review is beyond the scope of this work. We have chosen to include a sampling of publications that best represent the continuing trends and new ideas in the field. In keeping with past reviews on this subject1, we have broadened our scope to include fluid systems operating at high temperature and pressure, but below the critical point. Various terms have been applied to this state: sub-critical fluid extraction, pressurized liquid extraction, and accelerated solvent extraction. The term accelerated solvent extraction has been used by instrument manufacturers to refer to this process, but we will use the more descriptive term pressurized liquid extraction (PLE) to refer to these systems. Most of the research in the field is of an “evolutionary” rather than “revolutionary” nature. As in the previous review period, applications papers make up a majority of the published work. Pharmaceutical applications continue to be a strong theme. Most of the pharmaceutical work has centered on preparative, rather than analytical, separations. Chiral separations are an exception, as analytical scale separations of chiral compounds are an area of intense interest. Food and natural products represent the next largest body of work. Major themes are the isolation and characterization of high-value added foodstuffs, fragrances, and flavor compounds from novel natural materials or agricultural by-products. The areas of food, natural products, and pharmaceutical separation science converge in the area of so-called nutraceuticals. These are typically high-value products, either sold alone or as part of a fortified food, that

Full Text Available Process simulation involves the evaluation of output variables by the specification of input variables and process parameters. However, in a real process, input data and parameters cannot be known without uncertainty. This fact may limit the utilization of simulation results to predict plant behavior. In order to achieve a more realistic analysis, the procedure of stochastic simulation can be conducted. This technique is based on a large set of simulation runs where input variables and parameters are randomly selected according to adequate probability density functions. The objective of this work is to illustrate the application of a stochastic simulation procedure to the process of fractionation of orange essential oil, using supercritical carbon dioxide in a multistage extraction column. Analysis of the proposed example demonstrates the importance of the stochastic simulation to develop more reliable designs and operating conditions for a supercriticalfluid extraction process.

This is a method to reactively refine hydrocarbons, such as heavy oils with API gravities of less than 20.degree. and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure using a selectedfluid at supercritical conditions. The reaction portion of the method delivers lighter weight, more volatile hydrocarbons to an attached contacting device that operates in mixed subcritical or supercritical modes. This separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques. This method produces valuable products with fewer processing steps, lower costs, increased worker safety due to less processing and handling, allow greater opportunity for new oil field development and subsequent positive economic impact, reduce related carbon dioxide, and wastes typical with conventional refineries.

In the present paper a new extraction technique based on the combination of solid-phase/supercritical-fluid extraction (SPE/SFE) with subsequent reversed-phase HPLC is described. The SPE/SFE extractor was originally constructed from SPE-cartridge incorporated into the SFE extraction cell. Selected groups of benzoic acid derivatives (p-hydroxybenzoic, protocatechuic, gallic, vanillic and syringic acid), hydroxybenzaldehydes (4-hydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde) and cinnamic acid derivatives (o-coumaric, p-coumaric, caffeic, ferulic, sinapic and chlorogenic acid) were extracted. Cyclic addition of binary extraction solvent system based on methanol:water (1:1, v/v) and methanol/ammonia aqueous solution was used for extraction at 40MPa and 80 degrees C. The p-hydroxybenzoic, protocatechuic, vanillic, syringic, caffeic and chlorogenic acid; 4-hydroxybenzaldehyde and 3,4-dihydroxybenzaldehyde were identified by HPLC-electrospray mass spectrometry in SPE/SFE extracts of acid hydrolyzates of microalga (Spongiochloris spongiosa) and cyanobacterial strains (Spirulina platensis, Anabaena doliolum, Nostoc sp., and Cylindrospermum sp.). For the identification and quantification of the compounds the quasi-molecular ions [M-H](-) and specific fragments were analysed by quadrupole mass spectrometry analyzer. Our analysis showed that the microalgae and cyanobacteria usually contained phenolic acids or aldehydes at microg levels per gram of lyophilized sample. The proposed SPE/SFE extraction method would be useful for the analysis of different plant species containing trace amount of polar fraction of phenols.

Full Text Available Pure phase anatase TiO2 nanoparticles with sizes of 5–8 nm and varying crystallinity were synthesized in supercritical isopropanol/water using a continuous flow reactor. Their photodegradation of rhodamine B (RhB was evaluated under visible light irradiation. The as-prepared TiO2 nanoparticles show much higher photodegradation efficiencies than commercial Degussa P25 TiO2. Moreover, the photodegradation of RhB on the as-prepared TiO2 follows a different process from that on P25 TiO2, quicker N-deethylation and slower cleavage of conjugated chromophore structure. Based on PXRD, TEM, and BET measurements, these two photodegradation properties have been explained by the physicochemical properties of TiO2.

In order to assess the true impact of each single enantiomer of pharmacologically active compounds (PACs) in the environment, highly efficient, fast and sensitive analytical methods are needed. For the first time this paper focuses on the use of ultrahigh performance supercriticalfluid based chromatography coupled to a triple quadrupole mass spectrometer to develop multi-residue enantioselective methods for chiral PACs in environmental matrices. This technique exploits the advantages of supercriticalfluid chromatography, ultrahigh performance liquid chromatography and mass spectrometry. Two coated modified 2.5 μm-polysaccharide-based chiral stationary phases were investigated: an amylose tris-3,5-dimethylphenylcarbamate column and a cellulose tris-3-chloro-4-methylphenylcarbamate column. The effect of different chromatographic variables on chiral recognition is highlighted. This novel approach resulted in the baseline resolution of 13 enantiomers PACs (aminorex, carprofen, chloramphenicol, 3-N-dechloroethylifosfamide, flurbiprofen, 2-hydroxyibuprofen, ifosfamide, imazalil, naproxen, ofloxacin, omeprazole, praziquantel and tetramisole) and partial resolution of 2 enantiomers PACs (ibuprofen and indoprofen) under fast-gradient conditions (supercriticalfluid based chromatography coupled with tandem mass spectrometry.

A number of important processes utilizing supercriticalfluids have been either implemented or are emerging for extractions, separations and a wide range of cleaning applications. Supercriticalfluids can be reasonable solvents yet share many of the advantages of gases including miscibility with other gases (i.e. hydrogen and oxygen), low viscosities and high diffusivities. Carbon dioxide has the further advantages of being nontoxic, nonflammable, inexpensive and currently unregulated. The use of compressed gases, either as liquids or supercriticalfluids, as reaction media offers the opportunity to replace conventional hazardous solvents and also to optimize and potentially control the effect of solvent on chemical and material processing. The last several years has seen a significant growth in advances in chemical synthesis, catalytic transformations and materials synthesis and processing. The authors report on results from an exploratory program at Los Alamos National Laboratory aimed at investigating the use of dense phase fluids, particularly carbon dioxide, as reaction media for homogeneous, heterogeneous and phase-separable catalytic reactions in an effort to develop new, environmentally-friendly methods for chemical synthesis and processing. This approach offers the possibility of opening up substantially different chemical pathways, increasing selectivity at higher reaction rates, facilitating downstream separations and mitigating the need for hazardous solvents. Developing and understanding chemical and catalytic transformations in carbon dioxide could lead to greener chemistry at three levels: (1) Solvent replacement; (2) Better chemistry (e.g. higher reactivity, selectivity, less energy consumption); and (3) New chemistry (e.g. novel separations, use of COP{sub 2} as a C-1 source).

Full Text Available Supercriticalfluids are increasingly being used and promoted at a laboratory and pilot scale to produce high value, natural bioactives from biologically based raw materials. Supercritical CO2 is overwhelmingly the solvent of choice for these operations, but is largely limited to the processing of dry raw materials and the extraction of low polarity, low molecular weight compounds. The use of co-solvents and the use of alternative ânear-criticalâ extraction fluids such as dimethyl ether show potential to mitigate these limitations. Commercialisation of new supercritical extraction processes has arguably been limited because the supercritical extraction process has been developed in isolation of other processing steps necessary to achieve a successful product. This study reviews recent developments in integrated processing that incorporate the use of supercriticalfluids for bioseparations and in particular process schemes that produce high value natural bioactives. Integrated processes include prior operation (fermentation, extraction, enzyme pre-treatment, physical fractionation or size reduction followed by supercritical extraction or fractionation and processes in which operations are carried out in situ in supercriticalfluids (supercritical chromatography, enzymatic conversion, precipitation and coating of solutes. The use of co-solvents and alternative extraction solvents in these processes is discussed. Prospects for future developments are also discussed.

Full Text Available The performance analysis of a supercritical organic Rankine cycle system driven by exhaust heat using 18 organic working fluids is presented. Several parameters, such as the net power output, exergy efficiency, expander size parameter (SP, and heat exchanger requirement of evaporator and the condenser, were used to evaluate the performance of this recovery cycle and screen the working fluids. The results reveal that in most cases, raising the expander inlet temperature is helpful to improve the net power output and the exergy efficiency. However, the effect of the expander inlet pressure on those parameters is related to the expander inlet temperature and working fluid used. Either lower expander inlet temperature and pressure, or higher expander inlet temperature and pressure, generally makes the net power output more. Lower expander inlet temperature results in larger total heat transfer requirement and expander size. According to the screening criteria of both the higher output and the lower investment, the following working fluids for the supercritical ORC system are recommended: R152a and R143a.

Objective was to study solvation processes in pure and entrainer-modified supercriticalfluids. Specific topics were: Kinetics for solvation in supercritical media, influence on entrainers on solvation, reversibility of solvation, effects of solvation on intramolecular solute-solute interaction kinetics, and impact of fluid density on these processes. Time-resolved fluorescence spectroscopy was used as the main analytical tool. A summary is given of the 2.5 years' research.

The main objective of this research is to develop an equation of state that can be used to predict solubilities and tailor supercriticalfluid solvents for the extraction and processing of coal. To meet this objective we have implemented a two-sided. approach. First, we expanded the database of model coal compound solubilities in higher temperature fluids, polar fluids, and fluid mixtures systems. Second, the unique solute/solute, solute/cosolvent and solute/solvent intermolecular interactions in supercriticalfluid solutions were investigated using spectroscopic techniques. These results increased our understanding of the molecular phenomena that affect solubility in supercriticalfluids and were significant in the development of an equation of state that accurately reflects the true molecular makeup of the solution. (VC)

The physical and chemical characteristics of supercriticalfluids have prompted the development of supercriticalfluid chromatography (SFC) for the analysis of labile and less volatile compounds. High resolution chromatographic separations with efficiencies approaching those of gas chromatography and high speed analyses are possible in capillary SFC using pressure programming methods and narrow bore columns. Further refinement of the SFC-mass spectrometry interface (SFC-MS) provides the basis for extension to more polar fluid systems with greater solvating power and the selectivity and sensitivity of mass spectrometric detection. The use of polar modified fluids has been facilitated by advances in understanding of supercriticalfluid phase behavior. Fluid mixtures have been prepared for analysis of more polar, higher molecular weight analytes, that allow mild chromatographic temperatures and allow full exploitation of selectivity offered through control of fluid pressure (i.e., density). Continuing development of the SFC-MS interface has led to designs which can be near routinely applied with fluids such as CO/sub 2/, and providing enhanced transport of truly nonvolatile compounds to the mass spectrometer ionization regions. These advances also include an SFC interface to a high resolution, dual electric magnetic sector instrument, allowing supercriticalfluid solvents to be explited for on-line extraction-mass spectrometry for characterization of complex, often otherwise intractable, materials. 26 refs., 5 figs., 1 tab.

An oxy-combustor is provided which comprises a combustion vessel including at least one solid fuel slurry inlet port, at least one oxygen inlet port and at least one supercriticalfluid inlet port, wherein the combustion vessel is operable at an operating pressure of at least 1,100 psi; an interior of the combustion vessel comprises a combustion chamber and a supercriticalfluid infusion chamber surrounding at least a part of the combustion chamber, the supercriticalfluid infusion chamber and the combustion chamber are separated by a porous liner surrounding the combustion chamber, and the supercritical infusion chamber is located between the porous liner and an outer casing of the combustion vessel.

This report describes a new a continuous method for forming ethers, acetals and ketals using solid acid catalysts, DELOXAN ASP or AMBERLYST 15, and supercriticalfluid solvents. In the case of ether formation, the authors observe a high selectivity for linear alkyl ethers with little rearrangement to give branches ethers. Such rearrangement is common in conventional synthesis. The approach is effective for a range of n-alcohols up to n-octanol and also for the secondary alcohol 2-propanol. In the reaction of phenol with an alkylating agent, the continuous reaction can be tuned to give preferential O- or C-alkylation with up to 49% O-alkylation with supercritical propene. The authors also investigate the synthesis of a range of cyclic ethers and show an improved method for the synthesis of THF from 1,4-butandiol under very mild conditions.

Full Text Available Five cultivars of hop were extracted by the method of supercriticalfluid extraction using carbon dioxide (SFE–CO2 as extractant. The extraction (50 g of hop sample using a CO2 flow rate of 97.725 L/h was done in the two steps: 1. extraction at 150 bar and 40°C for 2.5 h (sample of series A was obtained and, after that, the same sample of hop was extracted in the second step: 2. extraction at 300 bar and 40 °C for 2.5 h (sample of series B was obtained. The Magnum cultivar was chosen for the investigation of the extraction kinetics. For the qualitative and quantitative analysis of the obtained hop extracts, the GC-MS method was used. Two of four themost common compounds of hop aroma (a-humulene and b-caryophyllene were detected in samples of series A. In addition, isomerized a-acids and a high content of b-acids were detected. The a-acids content in the samples of series B was the highest in the extract of the Magnum cultivar (it is a bitter variety of hop. The low contents of a-acids in all the other hop samples resulted in extracts with low a-acids content, i.e., that contents were under the prescribed a-acids content.

Small changes in temperature and pressure near the critical region induce dramatic changes in the density and solubility of supercriticalfluids, thereby facilitating the use of environmentally benign agents such as CO2 for their solvent and antisolvent properties in processing a wide variety of materials. While supercriticalfluid technologies have been in commercial use in the food and chromatography industries for several years, only recently has this technology made inroads in the formulation of drug delivery systems. This review summarizes some of the recent applications of supercriticalfluid technology in the preparation of drug delivery systems. Drugs containing polymeric particles, plain drug particles, solute-containing liposomes, and inclusion complexes of drug and carrier have been formulated using this technology. Also, polymer separation using this technology is enabling the selection of a pure fraction of a polymer, thereby allowing a more precise control of drug release from polymeric delivery systems.

The extraction behaviour of 10 ..mu..g samples of five pesticides and some related compounds from glass wool with supercritical CO/sub 2/ has been investigated under several conditions (10 MPa, 20 MPa extraction pressure, 313 K, dry and water saturated CO/sub 2/). The extraction fluid was decompressed over a line of little columns, filled with 3 ..mu.. Si60 or RP18, and the amount of deposited material was analyzed by HPLC for each of these columns. Due to the progressive pressure/density reduction along the line, the solubility diminishes and hence the compounds are deposited according to their polarity/vapor pressure earlier or later on the line. Thus extraction and prefractionation of compounds of different polarity take place in one sample preparation step.

Supercriticalfluids (SCFs) possess properties that are intermediate between liquids and gases. The combination of supercriticalfluid technology with advanced characterization techniques such as electron microscopy provided a practical and rewarding undergraduate laboratory experiment.

A numerical framework for simulating supercriticalfluids mixing with large density ratios is presented in the context of diesel sprays. Accurate modeling of real fluid effects on the fuel air mixture formation process is critical in characterizing engine combustion. Recent work (Dahms, 2013) has suggested that liquid fuel enters the chamber in a transcritical state and rapidly evolves to supercritical regime where the interface transitions from a distinct liquid/gas interface into a continuous turbulent mixing layer. In this work, the Peng Robinson EoS is invoked as the real fluid model due to an acceptable compromise between accuracy and computational tractability. Measurements at supercritical conditions are reported from the Constant Pressure Flow (CPF) chamber facility at the Army Research Laboratory. Mie and Schlieren optical spray diagnostics are utilized to provide time resolved liquid and vapor penetration length measurement. The quantitative comparison presented is discussed. Oak Ridge Associated Universities (ORAU).

The objective of this study was to investigate Fischer-Tropsch Synthesis (FTS) in the supercritical phase employing a commercial precipitated iron catalysts. As the supercriticalfluid the authors used propane and n-hexane. The catalyst had a nominal composition of 100 Fe/5 Cu/4.2 K/25 SiO{sub 2} on mass basis and was used in a fixed bed reactor under both normal (conventional) and supercritical conditions. Experimental data were obtained at different temperatures (235 C, 250 C, and 260 C) and synthesis gas feed compositions (H{sub 2}/CO molar feed ratio of 0.67, 1.0 and 2.0) in both modes of operation under steady state conditions. The authors compared the performance of the precipitated iron catalyst in the supercritical phase, with the data obtained in gas phase (fixed bed reactor) and slurry phase (STS reactor). Comparisons were made in terms of bulk catalyst activity and various aspects of product selectivity (e.g. lumped hydrocarbon distribution and olefin content as a function of carbon number). In order to gain better understanding of the role of intraparticle mass transfer during FTS under conventional or supercritical conditions, the authors have measured diffusivities of representative hydrocarbon products in supercriticalfluids, as well as their effective diffusion rates into the pores of catalyst at the reaction conditions. They constructed a Taylor dispersion apparatus to measure diffusion coefficients of hydrocarbon products of FTS in sub and supercritical ethane, propane, and hexane. In addition, they developed a tracer response technique to measure the effective diffusivities in the catalyst pores at the same conditions. Based on these results they have developed an equation for prediction of diffusion in supercriticalfluids, which is based on the rough hard sphere theory.

In concepts for supercritical water cooled reactors, the reactor core is cooled and moderated by water at supercritical pressures. The significant temperature dependence of the fluid properties of water requires an exact knowledge of the heat transfer mechanism to avoid fuel pin damages. Near the pseudo-critical point a deterioration of heat transfer might happen. Processes, that take place in this case, are not fully understood and are due to be examined systematically. In this paper a general overview on the properties of supercritical water is given, experimental observations of different authors will be reviewed in order to identify heat transfer phenomena and onset of occurrence. The conceptional design of a test rig to investigate heat transfer in the boundary layer will be discussed. Both, water and carbon dioxide, may serve as operating fluids. The loop, including instrumentation and safety devices, is shown and suitable measuring methods are described. (authors)

Consumers are aware of the processing techniques used to manufacture food and health supplements and are concerned about the impact of those processes on their health and the environment. Processes that use supercriticalfluids as an alternative to solvents that are used to extract nutrients and bio...

Full Text Available Supercritical carbon dioxide fluid is an alternative solvent for the water of the traditional dyeing. The solubility of dyestuff affects greatly the dyeing process. A theoretical model for predicting the dye solubility is proposed and verified experimentally. The paper concludes that the pressure has a greater impact on the dyestuff solubility than temperature, and an optimal dyeing condition is suggested for the highest distribution coefficient of dyestuff.

Supercriticalfluid extraction was used to recover organic and inorganic mercury species. Variations in pressure, water, methanol, and chelator create methods that allowed separation of inorganic from organic mercury species. When extracted using a compromised set of extraction conditions, the order of extraction was methyl, phenyl and inorganic mercury. For the individually optimized conditions, quantitative recoveries were observed. Level as low as 20 ppb were extracted and then determined using ICP.

Supercriticalfluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercriticalfluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop...

Extractions of a polycyclic aromatic hydrocarbon (PAH)-contaminated soil from a former manufactured gas plant site were performed with a Soxhlet apparatus (18 h), by pressurized liquid extraction (PLE) (50 min at 100°C), supercriticalfluid extraction (SFE) (1 h at 150°...

Extractions of a polycyclic aromatic hydrocarbon (PAH)-contaminated soil from a former manufactured gas plant site were performed with a Soxhlet apparatus (18 h), by pressurized liquid extraction (PLE) (50 min at 100°C), supercriticalfluid extraction (SFE) (1 h at 150°...

Full Text Available In this study, the total flavonoids from dandelion was extracted by supercritical CO2 and the total flavonoids content in the extract was investigated by the sodium nitrite-aluminum nitrate method with Rutin as a standard product. Single-factor experiments were carried out to map the effects of extraction pressure, temperature, time and entrainer amount on the yield of flavonoids. The orthogonal experiments on the optimum technology parameters demonstrated that the influence of the experimental conditions over the yield from high to low was: (a pressure, (b temperature, (c entrainer amount, (d time. The optimization result showed that under the conditions of 50°C, 35 MPa, 80 min and 4.0 mL/g entrainer amount, the yield of the preparative supercriticalfluid extraction was 4.974%.

A procedure is proposed for the supercriticalfluid extraction of all-trans-lycopene from tomato using carbon dioxide at 40 degrees C without modifier. The present method minimizes the risk of degradation via isomerization and oxidation of health-promoting ingredients, such as lycopene. The effect of different experimental variables on the solvating power of the supercriticalfluid was evaluated in terms of both the selectivity achievable in the process and the yield of the extraction of all-trans-lycopene. Satisfactory separations of the all-trans-lycopene isomers from the cis counterparts were achieved using a C(30) column. The obtained extract contained 88% all-trans-lycopene and 12% cis-lycopene.

Supercriticalfluid extraction (SFE), as a new green extraction technology, has been used in extracting various metal species. The solubilities of chelating agents and corresponding metal chelates are the key factors which influence the efficiency of SFE. Other main properties of them such as stability and selectivity are also reviewed. The extraction mechanisms of mainly used chelating agents are explained by typical examples in this paper. This is the important aspect of SFE of metal ions. Moreover, the extraction efficiencies of metal species also depend on other factors such as temperature, pressure, extraction time and matrix effect. The two main complexation methods namely in-situ and on-line chelating SFE are described in detail. As an efficient chelating agent, tributyl phosphate-nitric acid (TBP-HNO3) complex attracts much attention. The SFE of metal ions, lanthanides and actinides as well as organometallic compounds are also summarized. With the proper selection of ligands, high efficient extraction of metal species can be obtained. As an efficient sample analysis method, supercriticalfluid chromatography (SFC) is introduced in this paper. Recently, the extraction method combining ionic liquids (ILs) with supercriticalfluid has been becoming a novel technology for treating metal ions. The kinetics related to SFE of metal species is discussed with some specific examples.

The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercriticalfluids. Supercriticalfluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercriticalfluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect to the use of water as a supercriticalfluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”

A new method,which correlates rate constants of chemical reactions and density or pressure in supercriticalfluids,was developed.Based on the transition state theory and thermodynamic principles, the rate constant can be reasonably correlated with the density of the supercriticalfluid,and a correlation equation was obtained. Coupled with the equation of state (EOS) of a supercritical solvent,the effect of pressure on reaction rate constant could be represented.Two typical systems were used to test this method.The result indicates that this method is suitable for dilute supercriticalfluid solutions.

In a method of separating by extraction of coolants uranium and rare earth elements by using supercriticalfluid in a supercritical state and a hydrophobic organic chelating agent, a plurality of extraction steps having different extraction efficiencies are provided. As the fluid in the supercritical state, carbon dioxide, carbon monoxide, ammonia, sulfur tetrafluoride and nitrogen are mentioned. A hydrophobic organic chelating agent can form a chelating compound with uranium and rare earth elements, and the formed complex compounds are easily dissolved into the supercriticalfluid thereby enabling to provide an excellent extraction effect. A suitable hydrophobic organic chelating agent includes organic phosphor compounds, {beta}-diketone compounds and microcyclic compounds. Then, there can be provided an extraction method using a supercritical liquid as an extraction medium capable of successively separating uranium and rare earth elements selectively having high safety and performed safely and also performed in a case where a plurality of rare earth elements exist together. (N.H.)

Supercritical multicomponent fluid thermodynamics are often built from equations of state. We investigate mathematically such a construction of a Gibbsian thermodynamics compatible at low density with that of ideal gas mixtures starting from a pressure law. We further study the structure of chemical production rates obtained from nonequilibrium statistical thermodynamics. As a typical application, we consider the Soave-Redlich-Kwong cubic equation of state and investigate mathematically the corresponding thermodynamics. This thermodynamics is then used to study the stability of H2-O2-N2 mixtures at high pressure and low temperature as well as to illustrate the role of nonidealities in a transcritical H2-O2-N2 flame.

Supercriticalfluid extraction is used for producing bio-fuel from biomass. Supercriticalfluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercriticalfluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

Supercriticalfluid extraction is used for producing bio-fuel from biomass. Supercriticalfluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercriticalfluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

Rapid solubility screening in diverse supercriticalfluids (SCFs) was carried out via multiple solubility chambers with a trapping device and online ultraviolet (UV) detection. With this device, it was possible to rapidly study the solubility variations of multiple components in a mixture. Results from solubility studies have been used to develop efficient supercriticalfluid extraction (SFE) and supercriticalfluid chromatography (SFC) methods. After the investigation of solubilities of theophylline and caffeine in several neat organic solvents and SCFs, advantages of SFE over conventional organic solvent extraction were demonstrated with a model mixture of theophylline and caffeine. The highest solubility ratio of 1:40 (theophylline:caffeine) was observed in the SCF with 20% acetonitrile (MeCN), where a ratio of 1:11 was the highest in the neat organic solvents. A model mixture of theophylline:caffeine (85:15 w/w, caffeine as an impurity) was successfully purified by SFE by leveraging the highest solubility difference. The SCF with 20% MeCN selectively removed caffeine and left theophylline largely intact. Rapid SCF solubility screening was applied to development of SFE and SFC methods in a drug discovery environment. Two successful applications were demonstrated with proprietary Amgen compounds to either remove an achiral impurity before chiral purification or enhance chiral chromatographic throughput.

During the last few years, SupercriticalFluid Chromatography (SFC) has been emerged from an academic object of research to an important tool for the analytical chemist. Persuasive SFC-applications have been reported analyzing substrates with low volatilities, either due to high molecular weights or to high polarities, thermally or solvatolytically labile molecules, or analytes without chromophores or electroactive groups. Examples are oligomers and polymers up to a molecular weight of 10,000 g/mol, e.g., polysiloxanes, polyethers (nonionic surfactants), polyesters, polystyrenes and other vinyl polymers, polyenes etc. In addition, SFC is applicable to the analysis of several monomers. In the petroleum and coal industries, SFC was employed for the characterization of high boiling hydrocarbon mixtures as well as for group separations of alkanes, olefins, and aromatics. Due to the high solvent strength of supercriticalfluids, several pesticides, herbicides, and fungicides can be determined either separately or in combination with polar metabolites. Physiologically active substances often are thermally labile and polar at the same time. SFC has been successfully applied to the analysis of steroids, prostaglandins, cannabinoids and other drugs, flavours, and medicines. It is also well suited for analyzing natural or synthetic mono-, di-, and triglycerides. (orig.).

This text provides an introduction to supercriticalfluids with easy-to-use Excel spreadsheets suitable for both specialized-discipline (chemistry or chemical engineering student) and mixed-discipline (engineering/economic student) classes. Each chapter contains worked examples, tip boxes and end-of-the-chapter problems and projects. Part I covers web-based chemical information resources, applications and simplified theory presented in a way that allows students of all disciplines to delve into the properties of supercriticalfluids and to design energy, extraction and materials formation systems for real-world processes that use supercritical water or supercritical carbon dioxide. Part II takes a practical approach and addresses the thermodynamic framework, equations of state, fluid phase equilibria, heat and mass transfer, chemical equilibria and reaction kinetics of supercriticalfluids. Spreadsheets are arranged as Visual Basic for Applications (VBA) functions and macros that are completely (source code) ...

Polymer adhesion between two immiscible polymers is usually poor because there is little interpenetration of one polymer into the other at the interface. Increasing the width of the interfacial zone can enhance adhesion and mechanical properties. In principle, this can be accomplished by exposing heterogeneous polymer materials to a high-pressure fluid. The fluid can act as a common solvent and promote interpenetration. It also increases chain mobility at the interface, which helps to promote "welding" of the two polymers. A combination of the gradient theory of inhomogeneous systems and the Sanchez-Lacombe equation of state was used to investigate this phenomenon, especially the effect of the high compressibility of supercritical (SC) fluid on the compatibilization of two incompatible polymers. We calculate the interfacial density profile, interfacial thickness, and interfacial tension between the two polymers with and without the SC fluid. We find that the interfacial tension is decreased and the interfacial thickness is increased with high-pressure SC fluid for the ternary systems we have investigated. As the critical point is approached and the SC compressibility becomes large, no enhancement or deleterious effects on compatibilization were observed.

supercritical state. The fugacity of the solute in the supercriticalfluid can be evaluated using a cubic equation of state such as the Redlich - Kwong ...pro- gram was validated using available literature data for the solubility of naphthalene and of biphenyl in supercritical CO2. The applicability of...promising process using environmentally benign compressed gases as either solvents or anti-solvents is being investi- gated for applications in

Supercritical extraction (SFE), using primarily environmentally-benign carbon dioxide (CO{sub 2}) as the extraction agent, is reviewed with respect to its present status and future use. SFE was developed for analytical application in the mid 1980's in response to the desire to reduce the use of organic solvents in the laboratory environment and is becoming a standard method for the preparation and analysis of lipid-containing sample matrices. Currently, analytical SFE is predominately practiced in the off-line mode, using both sequential and parallel extraction modes. Depending on the instrumental configuration, the preparation of up to 24 samples can be accomplished on one instrument on a daily basis. Several other benefits can be achieved using SFE, such as the processing of thermally-sensitive analytes and rapid analyte extraction kinetics relative to extraction with liquid solvents. Examples are provided not only of the analytical SFE of oils and fats, but of volatile solutes from an array of sample types. Finally, the relevance of analytical SFE to processing with supercriticalfluids (SFs) is documented using examples from our own research involving a combinatorial approach to optimising processing conditions. (Author) 70 refs.

Full Text Available The extraction of carotenoids from crude palm oil was carried out in a dynamic (flow- through supercriticalfluid extraction system. The carotenoids obtained were quantified using off-line UV-visible spectrophotometry. The effects of operating pressure and temperature, flow rate of the supercritical carbon dioxide (SC-CO2, sample size of feed used on the solubility of palm carotenoids were investigated. The results showed that the extraction of carotenoids was governed by its solubility in the SC-CO2 and can be enhanced by increasing pressure at a constant temperature or decreasing temperature at a constant pressure. Increasing the flow rate and decreasing the sample size can reduce the extraction time but do not enhance the solubility. Palm carotenoids have very low solubility in SC-CO2 in the range of 1.31 x 10-4 g kg-1 to 1.58 x 10-3 g kg-1 for the conditions investigated in this study. The experimental data obtained were compared with those published by other workers and correlated by a density-based equation as proposed by Chrastil.

Beauvericin (BEA), a supercriticalfluid extraction with supercritical carbon dioxide from maize was investigated. Extraction efficiencies under several different extraction conditions were examined. Pressure, temperature, extraction time, organic modifier and water matrix content (10%) were investigated. The best extraction conditions were at a temperature of 60 degrees C, 3200psi, for 30min static extraction time and methanol as modifier solvent. Extraction recovery of 36% without modifier by adding water to the matrix in the extraction vessel (reproducibility relative standard deviations (R.S.D.)=3-5%) were recorded. Extraction recovery of 76.9% with methanol as co-solvent (reproducibility R.S.D.=3-5%) was obtained. Data shows that SFE gives a lower BEA recovery compared to conventional extraction protocol with organic solvents while SFE with modifier and conventional extraction yields are comparable. BEA extract contents were determined by high pressure liquid chromatography (HPLC) with a diode array detector (DAD) at 205nm and BEA peak confirmed by LC-MS. Acetonitrile-water as mobile phase and column C-18 were both tested. Instrumental and analytical parameters were optimized in the range linear interval from 1 to 500mgkg(-1) and reached a detection limit of 2ng.

We are investigating the use of supercriticalfluids to extract mineral and/or carbonaceous material from Martian surface soils and its igneous crust. Two candidate supercriticalfluids are carbon dioxide and water. The Martian atmosphere is composed mostly of carbon dioxide (approx. 95.3%) and could therefore provide an in-situ source of carbon dioxide. Water, although present in the Martian atmosphere at only approx. 0.03%, is also a candidate supercritical solvent. Previous work done with supercriticalfluids has focused primarily on their solvating properties with organic compounds. Interestingly, the first work reported by Hannay and Hogarth at a meeting of the Royal Society of London in 1879 observed that increasing or decreasing the pressure caused several inorganic salts e.g., cobalt chloride, potassium iodide, and potassium bromide, to dissolve or precipitate in supercritical ethanol. In high-pressure boilers, silica, present in most boiler feed waters, is dissolved in supercritical steam and transported as dissolved silica to the turbine blades. As the pressure is reduced the silica precipitates onto the turbine blades eventually requiring the shutdown of the generator. In supercritical water oxidation processes for waste treatment, dissolved salts present a similar problem. The solubility of silicon dioxide (SiO2) in supercritical water is shown. The solubility curve has a shape characteristic of supercritical systems. At a high pressure (greater than 1750 atmospheres) increasing the temperature results in an increase in solubility of silica, while at low pressures, less than 400 atm., the solubility decreases as temperature increases. There are only a few studies in the literature where supercriticalfluids are used in extractive metallurgy. Bolt modified the Mond process in which supercritical carbon monoxide was used to produce nickel carbonyl (Ni(CO)4). Tolley and Tester studied the solubility of titanium tetrachloride (TiCl4) in supercritical CO2

A new field of applications of compressed gases is the formation of solid particles with well-defined properties, e.g. the particle size, the particle size distribution, the particle shape, the specific surface area and free of solvent inclusions. It is possible to process moderately solids like energetic materials which are difficult to comminute due to their sensitivity to mechanical or thermal stress. The characteristics of compressed gases allow to vary the morphology of solid particles in a wide range. A pilot plant is presented, which has been built to prepare fine particles by the rapid expansion of supercritical solutions (RESS process) and precipitation by a compressed fluid antisolvent (PCA process). In this contribution the micronization of different energetic materials by the RESS and PCA processes will be under investigation. (orig.)

This research describes the development of a SupercriticalFluid Extraction (SFE) method to recover aflatoxin B1 from fortified soil. The effects of temperature, pressure, modifier (identity and percentage), and extraction type were assessed. Using the optimized SFE conditions, ...

This work presents a simple, rapid and reliable supercriticalfluid chromatography (SFC) method for a sensitive measurement of orotic acid in human urine. The samples were diluted with deionized water and analyzed directly without any pretreatment.

SupercriticalFluid Technology for Energy and Environmental Applications covers the fundamental principles involved in the preparation and characterization of supercriticalfluids (SCFs) used in the energy production and other environmental applications. Energy production from diversified resources - including renewable materials - using clean processes can be accomplished using technologies like SCFs. This book is focused on critical issues scientists and engineers face in applying SCFs to energy production and environmental protection, the innovative solutions they have found, and the challenges they need to overcome. The book also covers the basics of sub- and supercriticalfluids, like the thermodynamics of phase and chemical equilibria, mathematical modeling, and process calculations. A supercriticalfluid is any substance at a temperature and pressure above its critical point where distinct liquid and gas phases do not exist. At this state the compound demonstrates unique properties, which can be "fine...

This research describes the development of a SupercriticalFluid Extraction (SFE) method to recover aflatoxin B1 from fortified soil. The effects of temperature, pressure, modifier (identity and percentage), and extraction type were assessed. Using the optimized SFE conditions, ...

Objective was to study solvation processes in pure and entrainer-modified supercriticalfluids. Specific topics were: Kinetics for solvation in supercritical media, influence on entrainers on solvation, reversibility of solvation, effects of solvation on intramolecular solute-solute interaction kinetics, and impact of fluid density on these processes. Time-resolved fluorescence spectroscopy was used as the main analytical tool. A summary is given of the 2.5 years` research.

A novel approach to storing thermal energy with supercriticalfluids is being investigated, which if successful, promises to transform the way thermal energy is captured and utilized. The use of supercriticalfluids allows cost-affordable high-density storage with a combination of latent heat and sensible heat in the two-phase as well as the supercritical state. This technology will enhance penetration of several thermal power generation applications and high temperature water for commercial use if the overall cost of the technology can be demonstrated to be lower than the current state-of-the-art molten salt using sodium nitrate and potassium nitrate eutectic mixtures.

Biofuels are liquid or gaseous fuels that are predominantly produced from biomass for transport sector applications.As biofuels are renewable,sustainable,carbon neutral and environmentally benign,they have been proposed as promising alternative fuels for gasoline and diesel engines.This paper reviews state-of-the-art application of the supercriticalfluid(SCF)technique in biofuels production that includes biodiesel from vegetable oils via the transesterification process,bio-hydrogen from the gasification and bio-oil from the lique-faction of biomass,with biodiesel production as the main focus. The global biofuel situation and biofuel economics are also reviewed.The SCF has been shown to be a promising technique for future large-scale biofuel production,especially for biodiesel production from waster oil and fat.Compared with conventional biofuel production methods,the SCF technology possesses a number of advantages that includes fast inetics,high fuel production rate,ease of continuous operation and elimination of the necessity of catalysts.The harsh operation environment,i.e. the high temperature and high pressure,and its request on the materials and associated cost are the main concerns for its wide application.

Full Text Available One of the important trends in the food industry today is demand for natural antioxidants from plant material. Synthetic antioxidants such as butylated hydroxytoluene (BHT, and butylated hydroxyanisole (BHA are now being replaced by the natural antioxidants because of theirs possible toxicity and as they may act as promoters of carcinogens. The natural antioxidants may show equivalent or higher antioxidant activity than the endogenous or the synthetic antioxidants. Thus, great effort is being devoted to the search for alternative and cheap sources of natural antioxidants, as well as to the development of efficient and selective extraction techniques. The supercriticalfluid extraction (SFE with carbon dioxide is considered to be the most suitable method for producing natural antioxidants for the use in food industry. The supercritical extract does not contain residual organic solvents as in conventional extraction processes, which makes these products suitable for use in food, cosmetic and pharmaceutical industry. The recovery of antioxidants from plant sources involves many problematic aspects: choice of an adequate source (in terms of availability, cost, difference in phenolic content with variety and season; selection of the optimal recovery procedure (in terms of yield, simplicity, industrial application, cost; chemical analysis of extracts (for optimization purposes a fast colorimetric method is more preferable than a chromatographic one; evaluation of the antioxidant power (preferably by the different assay methods. The paper presents information about different operational methods for SFE of bioactive compounds from natural sources. It also includes the various reports on the antioxidant activity of the supercritical extracts from Lamiaceae herbs, in comparison with the activity of the synthetic antioxidants and the extracts from Lamiaceae herbs obtained by the conventional methods.

Full Text Available Supercriticalfluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercriticalfluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop extraction or removal of pesticides from rice, activity in supercritical extraction producing total extract from the raw material or different fractions by using the fractionated separation of beverages (rum, cognac, whisky, wine, beer cider, of citrus oils and of lipids (fish oils, tall oil were also discussed. The main interest is still for the extraction of natural raw materials producing food ingredients, nutraceuticals and phytopharmaceuticals but also cleaning purposes were tested such as the decontamination of soils the removal of residual solvents from pharmaceutical products, the extraction of flame retardants from electronic waste or precision degreasing and cleaning of mechanical and electronic parts. An increasing interest obviously exists for impregnation purposes based on supercriticalfluids behaviour, as well as for the dying of fibres and textiles. The production of fine particles in the micron and submicron range, mainly for pharmaceutical products is another important application of supercriticalfluids. Completely new products can be produced which is not possible under normal conditions. Supercriticalfluid technology has always had to compete with the widespread opinion that these processes are very expensive due to very high investment costs in comparison with classical low-pressure equipment. Thus the opinion is that these processes should be restricted to high-added value products. A cost estimation for different plant sizes and

The enthalpy of vaporization is the energy required to overcome intermolecular attractive forces and to expand the fluid volume against the ambient pressure when transforming a liquid into a gas. It diminishes for rising pressure until it vanishes at the critical point. Counterintuitively, we show that a latent heat is in fact also required to heat a supercriticalfluid from a liquid to a gaseous state. Unlike its subcritical counterpart, the supercritical pseudoboiling transition is spread over a finite temperature range. Thus, in addition to overcoming intermolecular attractive forces, added energy simultaneously heats the fluid. Then, considering a transition from a liquid to an ideal gas state, we demonstrate that the required enthalpy is invariant to changes in pressure for 0 intermolecular forces in the real fluid vapor during heating. At supercritical pressures, all of the transition occurs at non-equilibrium; for p -> 0 , all of the transition occurs at equilibrium.

Environmentally benign carbon dioxide offers significant potential in its supercriticalfluid phase to replace current reliance on a range of hazardous,relatively expensive and environmentally damaging organic solvents that are used on an extensive global basis.The unique combination of the physical properties of supercriticalfluids are being exploited and further researched to continue the development and establishment of high efficiency,compact plant to provide energy and water efficient manufacturing processes.This mini-review is focused on the use and potential applications of supercriticalfluid carbon dioxide for a selected range of key and emerging industrial processes as a sustainable alternative to totally eliminate or greatly reduce the requirement of numerous conventional organic solvents.Examples of the industries include:chemical extraction and purification,synthetic chemical reactions including polymerization and inorganic catalytic processes.Biochemical reactions involving enzymes,particle size engineering,textile dyeing and advanced material manufacture provide further illustrations of vital industrial activities where supercriticalfluid technology processes are being implemented or developed.Some aspects relating to the economics of sustainable supercriticalfluid carbon dioxide processes are also considered.

Environmentally benign carbon dioxide offers significant potential in its supercriticalfluid phase to replace current reliance on a range of hazardous, relatively expensive and environmentally damaging organic solvents that are used on an extensive global basis. The unique combination of the physical properties of supercriticalfluids are being exploited and further researched to continue the development and establishment of high efficiency, compact plant to provide energy and water efficient manufacturing processes. This mini-review is focused on the use and potential applications of supercriticalfluid carbon dioxide for a selected range of key and emerging industrial processes as a sustainable alternative to totally eliminate or greatly reduce the requirement of numerous conventional organic solvents. Examples of the industries include: chemical extraction and purification, synthetic chemical reactions including polymerization and inorganic catalytic processes. Biochemical reactions involving enzymes, particle size engineering, textile dyeing and advanced material manufacture provide further illustrations of vital industrial activities where supercriticalfluid technology processes are being implemented or developed. Some aspects relating to the economics of sustainable supercriticalfluid carbon dioxide processes are also considered.

Over the past two decades supercriticalfluids have been utilized as solvents for carrying out separations of materials as diverse as foods, polymers, pharmaceuticals, petrochemicals, natural products, and explosives. More recently they have been used for non-extractive applications such as recrystallization, deposition, impregnation, surface modification, and as a solvent alternative for precision parts cleaning. Today, supercriticalfluid extraction is being practiced in the foods and beverage industries; there are commercial plants for decaffeinating coffee and tea, extracting beer flavoring agents from hops, and separating oils and oleoresins from spices. Interest in supercriticalfluid processing of polymers has grown over the last ten years, and many new purification, fractionation, and even polymerization techniques have emerged. One of the most significant motivations for applying this technology to polymers has been increased performance demands. More recently, with increasing scrutiny of traditional solvents, supercriticalfluids, and in particular carbon dioxide, are receiving widespread attention as 'environmentally conscious' solvents. This paper describes several examples of polymers applications, including a few involving photoresists, which demonstrate that as next- generation advanced polymer systems emerge, supercriticalfluids are certain to offer advantages as cutting edge processing tools.

The first protocol for the analysis of isoflavones by supercriticalfluid chromatography is reported. Optimum results were obtained on an Acquity UPC(2) BEH 1.7 μm column, using a solvent gradient of supercritical carbon dioxide and methanol (with phosphoric acid as additive) for elution. The method enables the baseline separation of nine isoflavones (aglyca and glycosides) in 8 min, and is suitable for their quantitative determination in dietary supplements containing soy (Glycine max), red glover (Trifolium pratense) and kudzu (Pueraria lobata). Method validation confirmed that the assay is selective, linear (R(2)≥0.9994), accurate (recovery rates from 97.6 to 102.4%), as well as precise on the short- and long-term level (intra-day precision ≤2.1%), and shows an on-column detection limit of 0.2 ng and below. This, together with an excellent performance shown in the analysis of real samples, indicates that SFC is well suited for the fast and accurate determination of isoflavones in complex matrices. Disadvantages compared to the established approaches were not observed, so that SFC has to be considered in this case as an (at least) equivalent analytical alternative.

Full Text Available Supercriticalfluid extraction is an extraction process realized with supercriticalfluids, which are at a temperature and pressure above their critical temperature and critical pressure. This process has shown to be very efficient one for the isolation of different substances of medium molecular weights and molecules of relatively low polarity. The solubility of more polar substances in supercriticalfluids can be improved by the addition of small amounts of other polar solvents (cosolvent to the supercriticalfluids, which is the main solvent in extraction process. The advantage of supercritical extraction compared to other extraction procedures (the application of classical organic solvents hydrodistillation, distillation with steam is that SFE is usually performed at moderate temperature (e.g. with SF CO2 at 40-70°C so it can be applied for the separation of different substances which are thermally unstable and have a larger vapour pressure. All of these facts indicate that SFE is of special interest for the food and pharmaceutical industry.

Full Text Available As a new type of two-dimensional carbonaceous material, graphene has excellent physical properties and great application potential. The key problem to realize graphene industrialization is to find a large-scale preparing method of graphene with high quality and low cost. In this paper, the advantages and disadvantages of preparation methods for graphene were first reviewed, and then the mechanism, research status and characterization methods of supercriticalfluids exfoliated method were introduced in details. And the features of supercriticalfluids exfoliated method with the assistance of ultrasonication and pyrene-polymers were summarized. The advantages of supercriticalfluids exfoliated method are simple equipment, processing conditions easy to achieve and products with high quality, and a new way of thinking for the industrial production of graphene is provided.

Full Text Available Supercritical extraction (SFE, using primarily environmentally-benign carbon dioxide (CO2 as the extracting agent, is reviewed with respect to its present status and future use. SFE was developed for analytical application in the mid 1980âs in response to the desire to reduce the use of organic solvents in the laboratory environment and is becoming a standard method for the preparation and analysis of lipid-containing sample matrices. Currently, analytical SFE is predominately practiced in the off-line mode, using both sequential and parallel extraction modes. Depending on the instrumental configuration, the preparation of up to 24 samples can be accomplished on one instrument on a daily basis. Several other benefits can be achieved using SFE, such as the processing of thermally-sensitive analytes and rapid analyte extraction kinetics relative to extraction with liquid solvents. Examples are provided not only of the analytical SFE of oils and fats, but of volatile solutes from an array of sample types. Finally, the relevance of analytical SFE to processing with supercriticalfluids (SFs is documented using examples from our own research involving a combinatorial approach to optimising processing conditions.Este artículo revisa el presente y el uso futuro de la extracción con fluidos supercríticos (SFE, principalmente dióxido de carbono (CO2 benigno para el ambiente. La extracción con fluidos supercríticos se desarrolló como aplicación analítica a mediados de los años 80 como respuesta al deseo de reducir el uso de disolventes orgánicos en el ambiente del laboratorio, y se está convirtiendo en un método estándar con respecto a la preparación y análisis de muestras conteniendo lípidos. Actualmente, la analítica de SFE es predominantemente aplicada en modo âoff-lineâ, usando modos de extracción secuenciales y paralelos. Dependiendo de la configuración de la instrumentación, se pueden llegar a preparar diariamente

Having similar densities as liquids but with viscosities up to 20 times lower (higher diffusion coefficients), supercritical CO2 is the ideal (co-)solvent for fast and/or highly efficient separations without mass-transfer limitations or excessive column pressure drops. Whereas in liquid chromatography the flow remains laminar in both the packed bed and tubing, except in extreme cases (e.g. in a 75 μm tubing, pure acetonitrile at 5 ml/min), a supercriticalfluid can experience a transition from laminar to turbulent flow in more typical operation modes. Due to the significant lower viscosity, this transition for example already occurs at 1.3 ml/min for neat CO2 when using connection tubing with an ID of 127 μm. By calculating the Darcy friction factor, which can be plotted versus the Reynolds number in a so-called Moody chart, typically used in fluid dynamics, higher values are found for stainless steel than PEEK tubing, in agreement with their expected higher surface roughness. As a result turbulent effects are more pronounced when using stainless steel tubing. The higher than expected extra-column pressure drop limits the kinetic performance of supercriticalfluid chromatography and complicates the optimization of tubing ID, which is based on a trade-off between extra-column band broadening and pressure drop. One of the most important practical consequences is the non-linear increase in extra-column pressure drop over the tubing downstream of the column which leads to an unexpected increase in average column pressure and mobile phase density, and thus decrease in retention. For close eluting components with a significantly different dependence of retention on density, the selectivity can significantly be affected by this increase in average pressure. In addition, the occurrence of turbulent flow is also observed in the detector cell and connection tubing. This results in a noise-increase by a factor of four when going from laminar to turbulent flow (e.g. going

The reported work demonstrates and discusses the effect of supercriticalfluid density (pressure and temperature of supercriticalfluid carbon dioxide) on particle size and distribution using the supercritical antisolvent (SAS) method in the purpose of drug encapsulation. In this study, paracetamol was encapsulated inside L-polylactic acid, a semicrystalline polymer, with different process parameters, including pressure and temperature, using the SAS process. The morphology and particle size of the prepared nanoparticles were determined by scanning electron microscopy and transmission electron microscopy. The results revealed that increasing temperature enhanced mean particle size due to the plasticizing effect. Furthermore, increasing pressure enhanced molecular interaction and solubility; thus, particle size was reduced. Transmission electron microscopy images defined the internal structure of nanoparticles. Thermal characteristics of nanoparticles were also investigated via differential scanning calorimetry. Furthermore, X-ray diffraction pattern revealed the changes in crystallinity structure during the SAS process. In vitro drug release analysis determined the sustained release of paracetamol in over 4 weeks.

A method combining supercritical carbon dioxide (SC-CO2) and high power ultrasound (HPU) has been developed and tested for microbial/enzyme inactivation purposes, at different process conditions for both liquid and solid matrices. In culture media, using only SC-CO2, the inactivation rate of E. coli and S. cerevisiae increased with pressure and temperature; and the total inactivation (7-8 log-cycles) was attained after 25 and 140 min of SC-CO2 (350 bar, 36 °C) treatment, respectively. Using SC-CO2+HPU, the time for the total inactivation of both microorganisms was reduced to only 1-2 min, at any condition selected. The SC-CO2+HPU inactivation of both microorganisms was slower in juices (avg. 4.9 min) than in culture media (avg. 1.5 min). In solid samples (chicken, turkey ham and dry-cured pork cured ham) treated with SC-CO2 and SC-CO2+HPU, the inactivation rate of E. coli increased with temperature. The application of HPU to the SC-CO2 treatments accelerated the inactivation rate of E. coli and that effect was more pronounced in treatments with isotonic solution surrounding the solid food samples. The application of HPU enhanced the SC-CO2 inactivation mechanisms of microorganisms, generating a vigorous agitation that facilitated the CO2 solubilization and the mass transfer process. The cavitation generated by HPU could damage the cell walls accelerating the extraction of vital constituents and the microbial death. Thus, using the combined technique, reasonable industrial processing times and mild process conditions could be used which could result into a cost reduction and lead to the minimization in the food nutritional and organoleptic changes.

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercriticalfluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercriticalfluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated .beta.-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated .beta.-diketone and a trialkyl phosphate, or a fluorinated .beta.-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated .beta.-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercriticalfluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercriticalfluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercriticalfluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated {beta}-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated {beta}-diketone and a trialkyl phosphate, or a fluorinated {beta}-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated {beta}-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercriticalfluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs.

Full Text Available Nanofibers have a wide range of applications, including filtration and biomedical engineering. Porous or hollow fibers with large surface-to-volume ratios are more popular in some fields than the common nanofibers. Porous nanofibers can be obtained through electrospinning with highly volatile solvents or through special treatment following electrospinning. A new process where electrospinning is conducted in supercritical or near-critical CO2 to produce porous or hollow nanofibers has been summarized. In addition, a process entailing compressed N2-assisted electrospinning was attempted to produce PVP nanofibers in this work, but it was proved to be unsuccessful. Since the fiber morphologies are dependent on the phase behavior of organic solvents in supercriticalfluids, ASPEN PLUS 2006 was used to simulate the phase equilibrium of the solvent-supercriticalfluid system to explain why porous or hollow fibers can be obtained in compressed CO2, but not in compressed N2.

Binary diffusion coefficient D{sub 12} in supercritical carbon dioxide were determined in a SupercriticalFluid Chromatography (SFC) apparatus by the peak broadening method (PBM). Some cyclic and linear ketones were investigated as a function of pressure between 9.5 and 18 MPa at about 314 K corresponding to densities form 513 to 820 kg m{sup -3}. The resulting D{sub 12} values are of the order of 10{sup -8} m{sup 2} s{sup -1} and lnD{sub 12} decreases about linearly with increasing density {rho} of the CO{sub 2}. (orig.).

Benzene, toluene, ethylbenzene, o-, m-, and p-xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs) were extracted from eight manufactured gas plant (MGP) soils from sites that had been abandoned for several decades. Supercriticalfluid extraction (SFE) with pure carbon dioxide demonstrated the presence of BTEX compounds that were highly sequestered in both coal gas and oil gas MGP soils and soots. Benzene was generally the slowest compound to extract from all samples and was even more difficult to extract than most two- to five-ring PAHs found on the same samples. Since the solubility of benzene in carbon dioxide is 2-5 orders of magnitude higher than the solubilities of PAHs, these results demonstrate that benzene was more tightly sequestered than toluene, ethylbenzene, xylenes, or the multi-ring PAHs. Additional evidence for very tight binding was based on the fact that BTEX concentrations determined using either SFE or with methylene chloride sonication were much higher than those obtained by the U.S. EPA purge-and-trap method, especially for benzene (whose concentration was underestimated by as much as 1000-fold by the EPA method). However, soil/water desorption showed little benzene mobility, and Kd values for benzene were 1-2 orders of magnitude higher than those calculated based on literature sorption K(OC) values. These results indicate that environmentally relevant concentrations of benzene may be better represented by mild extraction methods than by methods capable of extracting tightly bound benzene.

High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of SupercriticalFluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercriticalfluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercriticalfluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical research and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercriticalfluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprinting.

Full Text Available High performance specifications and unique functionality of chromatographic techniques is a demand of pharmaceutical industry and research. This leads to the origin of SupercriticalFluid Chromatography (SFC. It is a rapidly expanding analytical technique. The main feature that differentiates SFC from other chromatographic techniques is the replacement of either the liquid or gas mobile phase with a supercriticalfluid mobile phase. It is considered a hybrid of GC and LC technique. High diffusion coefficient and low viscosity of supercriticalfluids is responsible for high speed analysis, high efficiency and high sensitivity. Low mobile-phase flow rate, density programming and compatability with GC and LC detectors make SFC a versatile chromatographic technique in analytical re-search and development. It has a unique characteristic of analyzing thermo labile or non-volatile substances. This review highlights the role of supercriticalfluid chromatography in the separation of polymers, thermally labile pesticides, fatty acids, metal chelates and organometallic compounds, chiral and achiral molecules, identification and analysis of polar samples, explosives, drugs of abuse and application of SFC in forensic science (fingerprint-ing.

The task of lipid analysis has always challenged separation scientists, and new techniques in chromatography were often developed for the separation of lipids; however, no single technique or methodology is yet capable of affording a comprehensive screening of all lipid species and classes. This review acquaints the role of supercriticalfluid chromatography within the field of lipid analysis, from the early developed capillary separations based on pure CO2 , to the most recent techniques employing packed columns under subcritical conditions, including the niche multidimensional techniques using supercriticalfluids in at least one of the separation dimensions. A short history of supercriticalfluid chromatography will be introduced first, from its early popularity in the late 1980s, to the sudden fall and oblivion until the last decade, experiencing a regain of interest within the chromatographic community. Afterwards, the subject of lipid nomenclature and classification will be briefly dealt with, before discussing the main applications of supercriticalfluid chromatography for food analysis, according to the specific class of lipids.

A new method of heat transfer prediction in supercriticalfluids is presented. Emphasis is put on the simplicity of the correlation structure and its explicit coupling with physical phenomena. Assessment of qualitative behaviour of heat transfer is conducted based on existing test data and experience gathered from open literature. Based on phenomenological analysis and test data evaluation, a single dimensionless number, the acceleration number, is introduced to correct the deviation of heat transfer from its conventional behaviour, which is predicted by the Dittus-Boelter equation. The new correlation structure excludes direct dependence of heat transfer coefficient on wall surface temperature and eliminates possible numerical convergence. The uncertainty analysis of test data provides information about the sources and the levels of uncertainties of various parameters and is highly required for the selection of both the dimensionless parameters implemented into the heat transfer correlation and the test data for the development and validation of new correlations. Comparison of various heat transfer correlations with the selected test data shows that the new correlation agrees better with the test data than other correlations selected from the open literature.

Highly contaminated (with PAHs) topsoils were extracted with supercritical CO2 to determine the feasibility and mechanism of supercriticalfluid extraction (SFE). Effect of SCF density, temperature, cosolvent type and amount, and of slurrying the soil with water were ...

Enantiomeric pairs of triticonazole have been successfully separated by supercriticalfluid chromatography coupled with a tris(3,5-dimethylphenylcarbamoyl) cellulose-coated chiral stationary phase in this work. The effects of co-solvent, dissolution solvent, flow rate, backpressure, and column temperature have been studied in detail with respect to retention, selectivity, and resolution of triticonazole. As indicated, the co-solvents mostly affected the retention factors and resolution, due to the different molecular structure and polarity. In addition, the dissolution solvents, namely, chloromethanes and alcohols, have been also important for enantioseparation because of the different interaction with stationary phase. Higher flow rate and backpressure led to faster elution of the triticonazole molecules, and the change of column temperature showed slight effect on the resolution of triticonazole racemate. Moreover, a comparative separation experiment between supercriticalfluid chromatography and high performance liquid chromatography revealed that chiral supercriticalfluid chromatography gave the 3.5 times value of Rs /tR2 than high performance liquid chromatography, which demonstrated that supercriticalfluid chromatography had much higher separation efficiency.

A method for predicting the viscosity of supercritical, multicomponent fluid mixtures, at any density, from the zero-density viscosity of pure components is presented. The method is based upon the results for a rigid-sphere model, suitably interpreted to apply to real fluids, and on the finding that the excess viscosity of pure supercriticalfluids can be adequately described by a density function independent of temperature. The density range of the method extends to twice the critical density of the pure component with the smallest critical density. The only exception is for the methane-rich mixtures where the mixture density should not exceed 12000 mol{center_dot}m{sup {minus}3}. The uncertainty ascribed to the predictions made by this method is of the order of {+-}5%.

Exciting opportunities exist for the application of supercriticalfluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercriticalfluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as the model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane.

Exciting opportunities exist for the application of supercriticalfluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercriticalfluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as the model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane.

This article serves as an overview, introducing the currently popular area of supercriticalfluids and their uses in food biotechnology. Within each application, and wherever possible, the basic principles of the technique, as well as a description of the history, instrumentation, methodology, uses, problems encountered, and advantages over the traditional, non-supercritical methods are given. Most current commercial application of the supercritical extraction involve biologically-produced materials; the technique may be particularly relevant to the extraction of biological compounds in cases where there is a requirement for low-temperature processing, high mass-transfer rates, and negligible carrying over of the solvent into the final product. Special applications to food processing include the decaffeination of green coffee beans, the production of hops extracts, the recovery of aromas and flavors from herbs and spices, the extraction and fractionation of edible oils, and the removal of contaminants, among others. New advances, in which the extraction is combined with reaction or crystallization steps, may further increase the attractiveness of supercriticalfluids in the bioprocess industries. To develop and establish a novel and effective alternative to heating treatment, the lethal action of high hydrostatic pressure CO(2) on microorganisms, with none or only a minimal heating process, has recently received a great deal of attention.

The phenomena of supercriticalfluid extraction (SFE) and its reverse effect, which is known as retrograde condensation (RC), have found new and important applications in industrial separation of chemical compounds and recovery and processing of natural products and fossil fuels. Full-scale industrial utilization of SFE/RC processes requires knowledge about thermodynamic and transport characteristics of the asymmetric mixtures involved and the development of predictive modeling and correlation techniques for performance of the SFE/RC system under consideration. In this report, through the application of statistical mechanical techniques, the reasons for the lack of accuracy of existing predictive approaches are described and they are improved. It is demonstrated that these techniques also allow us to study the effect of mixed supercritical solvents on the solubility of heavy solutes (solids) at different compositions of the solvents, pressures, and temperatures. Fluid phase equilibrium algorithms based on the conformal solution van der Waals mixing rules and different equations of state are presented for the prediction of solubilities of heavy liquid in supercritical gases. It is shown that the Peng-Robinson equation of state based on conformal solution theory can predict solubilites of heavy liquid in supercritical gases more accurately than the van der Waals and Redlich-Kwong equations of state.

The role of different contributions to intermolecular interactions on the thermodynamic properties of supercriticalfluids is investigated. Molecular dynamics simulation results are reported for the energy, pressure, thermal pressure coefficient, thermal expansion coefficient, isothermal and adiabatic compressibilities, isobaric and isochoric heat capacities, Joule-Thomson coefficient, and speed of sound of fluids interacting via both the Lennard-Jones and Weeks-Chandler-Andersen potentials. These properties were obtained for a wide range of temperatures, pressures, and densities. For each thermodynamic property, an excess value is determined to distinguish between attraction and repulsion. It is found that the contributions of intermolecular interactions have varying effects depending on the thermodynamic property. The maxima exhibited by the isochoric and isobaric heat capacities, isothermal compressibilities, and thermal expansion coefficient are attributed to interactions in the Lennard-Jones well. Repulsion is required to obtain physically realistic speeds of sound and both repulsion and attraction are necessary to observe a Joule-Thomson inversion curve. Significantly, both maxima and minima are observed for the isobaric and isochoric heat capacities of the supercritical Lennard-Jones fluid. It is postulated that the loci of these maxima and minima converge to a common point via the same power law relationship as the phase coexistence curve with an exponent of β = 0.32. This provides an explanation for the terminal isobaric heat capacity maximum in supercriticalfluids.

CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercriticalfluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.

The use of supercriticalfluid chromatography for natural product analysis as well as underlying theoretical mechanisms and instrumental requirements are summarized in this review. A short introduction focusing on the historical development of this interesting separation technique is followed by remarks on the current instrumental design, also describing possible detection modes and useable stationary phases. The overview on relevant applications is grouped based on their basic intention, may it be (semi)preparative or purely analytical. They indicate that supercriticalfluid chromatography is still primarily considered for the analysis of nonpolar analytes like carotenoids, fatty acids, or terpenes. The low polarity of supercritical carbon dioxide, which is used with modifiers almost exclusively as a mobile phase today, combined with high efficiency and fast separations might explain the popularity of supercriticalfluid chromatography for the analysis of these compounds. Yet, it has been shown that more polar natural products (e.g., xanthones, flavonoids, alkaloids) are separable too, with the same (if not superior) selectivity and reproducibility than established approaches like HPLC or GC.

This book investigates the unique hydrodynamics and heat transfer problems that are encountered in the vicinity of the critical point of fluids. Emphasis is given on weightlessness conditions, gravity effects and thermovibrational phenomena. Near their critical point, fluids indeed obey universal behavior and become very compressible and expandable. Their comportment, when gravity effects are suppressed, becomes quite unusual. The problems that are treated in this book are of interest to students and researchers interested in the original behavior of near-critical fluids as well as to engineers that have to manage supercriticalfluids. A special chapter is dedicated to the present knowledge of critical point phenomena. Specific data for many fluids are provided, ranging from cryogenics (hydrogen) to high temperature (water). Basic information in statistical mechanics, mathematics and measurement techniques is also included. The basic concepts of fluid mechanics are given for the non-specialists to be able to ...

Full Text Available The recent development of world is being adversely affected by the scarcity of power and energy. To survive in the next generation, it is thus necessary to explore the non-conventional energy sources and efficiently consume the available sources. For efficient exploitation of the existing energy sources, a great scope lies in the use of Rankin cycle-based thermal power plants. Today, the gross efficiency of Rankin cycle-based thermal power plants is less than 28% which has been increased up to 40% with reheating and regenerative cycles. But, it can be further improved up to 47% by using supercritical power plant technology. Supercritical power plants use supercritical boilers which are able to withstand a very high temperature (650-720˚C and pressure (22.1 MPa while producing superheated steam. The thermal efficiency of a supercritical boiler greatly depends on the material of its different components. The supercritical boiler material should possess high creep rupture strength, high thermal conductivity, low thermal expansion, high specific heat and very high temperature withstandability. This paper considers a list of seven supercritical boiler materials whose performance is evaluated based on seven pivotal criteria. Given the intricacy and difficulty of this supercritical boiler material selection problem having interactions and interdependencies between different criteria, this paper applies fuzzy analytic network process to select the most appropriate material for a supercritical boiler. Rene 41 is the best supercritical boiler material, whereas, Haynes 230 is the worst preferred choice.

Supercriticalfluid extraction (SFE) of plutonium and americium from soil was successfully demonstrated using supercriticalfluid carbon dioxide solvent augmented with organophosphorus and beta-diketone complexants. Spiked Idaho soils were chemically and radiologically characterized, then extracted with supercriticalfluid carbon dioxide at 2,900 psi and 65 C containing varying concentrations of tributyl phosphate (TBP) and thenoyltrifluoroacetone (TTA). A single 45 minute SFE with 2.7 mol% TBP and 3.2 mol% TTA provided as much as 88% {+-} 6.0 extraction of americium and 69% {+-} 5.0 extraction of plutonium. Use of 5.3 mol% TBP with 6.8 mol% of the more acidic beta-diketone hexafluoroacetylacetone (HFA) provided 95% {+-} 3.0 extraction of americium and 83% {+-} 5.0 extraction of plutonium in a single 45 minute SFE at 3,750 psi and 95 C. Sequential chemical extraction techniques were used to chemically characterize soil partitioning of plutonium and americium in pre-SFE soil samples. Sequential chemical extraction techniques demonstrated that spiked plutonium resides primarily (76.6%) in the sesquioxide fraction with minor amounts being absorbed by the oxidizable fraction (10.6%) and residual fractions (12.8%). Post-SFE soils subjected to sequential chemical extraction characterization demonstrated that 97% of the oxidizable, 78% of the sesquioxide and 80% of the residual plutonium could be removed using SFE. These preliminary results show that SFE may be an effective solvent extraction technique for removal of actinide contaminants from soil.

Supercriticalfluid extraction (SFE), which has received much interest in its use and further development for industrial applications, is a method that offers some advantages over conventional methods, especially for the palm oil industry. SC-CO2 refers to supercriticalfluid extraction (SFE) that uses carbon dioxide (CO2) as a solvent which is a nontoxic, inexpensive, nonflammable, and nonpolluting supercriticalfluid solvent for the extraction of natural products. Almost 100% oil can be ext...

Highlights: • Subchannel analysis with turbulent mixing rate law of supercritical pressure fluid (SPF) is carried out. • Turbulent mixing rate is enhanced, compared with that calculated by the law of pressurized water reactor (PWR). • Increase in maximum cladding surface temperature (MCST) is smaller comparing with PWR model. • The sensitivities of MCST on non-uniformity of subchannel area and power peaking are reduced by using SPF model. - Abstract: The subchannel analysis with turbulent mixing rate law of supercritical pressure fluid (SPF) is carried out for supercritical-pressurized light water cooled and moderated reactor (Super LWR). It is different from the turbulent mixing rate law of pressurized water reactor (PWR), which is widely adopted in Super LWR subchannel analysis study, the density difference between adjacent subchannels is taken into account for turbulent mixing rate law of SPF. MCSTs are evaluated on three kinds of fuel assemblies with different pin power distribution patterns, gap spacings and mass flow rates. Compared with that calculated by employing turbulent mixing rate law of PWR, the increase in MCST is smaller even when peaking factor is large and gap spacing is uneven. The sensitivities of MCST on non-uniformity of the subchannel area and power peaking are reduced.

Full Text Available This article reviews the fundamentals of supercriticalfluid (SCF science and moves on to the biotechnological applications of them e.g. removal of biostatic agents from fermentation broths, SCF disruption of microorganisms, destruction of industrial waste, the gas-antisolvent crystallization and micron-size particle formation. Also gaining ground is enzymatic catalysis in supercritical carbon dioxide (SC-CO2, which offers the possibility of integrated synthesis product recovery processes. The paper is structured as follows: first, the effects of dense SC-CO2 on the extraction of biomaterials and disruption of cells are thoroughly reported and discussed. Then the application of SC-CO2 in particle formation and modifications of biopolymers and enzymes are described. In general, the article is focused on potential bio-industrial applications and future research needs of the SCF technology. Keywords: Biotechnology, SupercriticalFluids (SCF, disruption, inactivation, extraction, downstream, particle formation Received: 10 October 2009 / Received in revised form: 30 January 2010, Accepted: 30 January 2010, Published online: 10 March 2010

Supercritical carbon dioxide (SCCO(2)) is an ecofriendly supercriticalfluid that is chemically inert, nontoxic, noninflammable and nonpolluting. As a green material, SCCO(2) has desirable properties such as high density, low viscosity and high diffusivity that make it suitable for use as a solvent in supercriticalfluid extraction, an effective and environment-friendly analytical method, and as a mobile phase for supercriticalfluid chromatography, which facilitates high-throughput, high-resolution analysis. Furthermore, the low polarity of SCCO(2) is suitable for the extraction and analysis of hydrophobic compounds. The growing concern surrounding environmental pollution has triggered the development of green analysis methods based on the use of SCCO(2) in various laboratories and industries. SCCO(2) is becoming an effective alternative to conventional organic solvents. In this review, the usefulness of SCCO(2) in supercriticalfluid extraction and supercriticalfluid chromatography for the extraction and analysis of lipids is described.

Full Text Available Nowadays, the use of Organic Rankine Cycle (ORC in decentralised applications is linked with the fact that this process allows to use low temperature heat sources and offers an advantageous efficiency in small-scale applications. Many state of the art applications like geothermal and biomass fired power plants as well as new applications like solar desalination with reverse osmosis, waste heat recovery from biogas digestion plants or micro-Combined Heat and Power (micro-CHP systems can successfully use the ORC process. The investigation of supercritical parameters in ORC applications seems to bring promising results in decentralised energy production. This paper presents the results from the simulation of the ORC process in normal and supercriticalfluid parameters and discusses the efficiency variation in various applications.

Extraction or leaching of solute from natural solid material is a mass transfer process involving dissolution or release of solutes from a solid matrix. Interaction between the solute and solid matrix often influences the supercriticalfluid extraction process. A model accounting for the solute-solid interaction as well as mass transfer is developed. The BET equation is used to incorporate the interaction and the solubility of solutes into the local equilibrium in the model. Experimental data for the supercritical extraction of essential oil and cuticular wax from peppermint leaves are successfully analyzed by the model. The effects of parameters on the extraction behavior are demonstrated to illustrate the concept of the model. 18 refs., 5 figs., 1 tab.

This thesis describes the application of supercritical CO sub 2 to the modification and processing of polymeric materials. Chapter 1 begins by outlining the physical properties of supercriticalfluids (SCF's) and the characteristic signatures of critical point phase transitions. This chapter then goes on to describe some of the current applications of SCF's and the advantages that can be gained by working in such media with particular reference to applications involving polymers. Whilst SCF's may offer several advantages compared to conventional liquid solvents, the switch to a SCF process is by no means a straightforward task and requires consideration of several factors in its development. Such considerations are discussed in the first part of chapter 2, again with particular reference to the modification and processing of polymers. Chapter 3 details the preliminary results obtained from experiments performed with the new high-pressure IR cell; initial experiments were carried out to study the effectiveness...

Impurity profiling of organic products that are synthesized as possible drug candidates requires complementary analytical methods to ensure that all impurities are identified. Supercriticalfluid chromatography (SFC) is a very useful tool to achieve this objective, as an adequate selection of stationary phases can provide orthogonal separations so as to maximize the chances to see all impurities. In this series of papers, we have developed a method for achiral SFC-MS profiling of drug candidates, based on a selection of 160 analytes issued from Servier Research Laboratories. In the first part of this study, focusing on mobile phase selection, a gradient elution with carbon dioxide and methanol comprising 2% water and 20mM ammonium acetate proved to be the best in terms of chromatographic performance, while also providing good MS response [1]. The objective of this second part was the selection of an orthogonal set of ultra-high performance stationary phases, that was carried out in two steps. Firstly, a reduced set of analytes (20) was used to screen 23 columns. The columns selected were all 1.7-2.5μm fully porous or 2.6-2.7μm superficially porous particles, with a variety of stationary phase chemistries. Derringer desirability functions were used to rank the columns according to retention window, column efficiency evaluated with peak width of selected analytes, and the proportion of analytes successfully eluted with good peak shapes. The columns providing the worst performances were thus eliminated and a shorter selection of columns (11) was obtained. Secondly, based on 160 tested analytes, the 11 columns were ranked again. The retention data obtained on these columns were then compared to define a reduced set of the best columns providing the greatest orthogonality, to maximize the chances to see all impurities within a limited number of runs. Two high-performance columns were thus selected: ACQUITY UPC(2) HSS C18 SB and Nucleoshell HILIC.

The production of integrated circuits (IC's) involves a number of discrete steps which utilize hazardous or regulated solvents and generate large waste streams. ES&H considerations associated with these chemicals have prompted a search for alternative, more environmentally benign solvent systems. An emerging technology for conventional solvent replacement is the use of supercriticalfluids based on carbon dioxide (CO{sub 2}). Research work, conducted at Los Alamos in conjunction with the Hewlett-Packard Company, has lead to the development of a CO{sub 2}-based supercriticalfluid treatment system for the stripping of hard-baked photoresists. This treatment system, known as Supercritical CO{sub 2} Resist Remover, or CORR, uses a two-component solvent composed of a nonhazardous, non-regulated compound, dissolved in supercritical CO{sub 2}. The solvent/treatment system has been successfully tested on metallized Si wafers coated with negative and positive photoresist, the latter both before and after ion-implantation. A description of the experimental data will be presented. Based on the initial laboratory results, the project has progressed to the design and construction of prototype, single-wafer photoresist-stripping equipment. The integrated system involves a closed-loop, recirculating cycle which continuously cleans and regenerates the CO{sub 2}, recycles the dissolved solvent, and separates and concentrates the spent resist. The status of the current design and implementation strategy of a treatment system to existing IC fabrication facilities will be discussed. Additional remarks will be made on the use of a SCORR-type system for the cleaning of wafers prior to processing.

The environmentally benign, non-toxic, non-flammable fluids water and carbon dioxide (CO2) are the two most abundant and inexpensive solvents on earth. Emulsions of these fluids are of interest in many industrial processes, as well as CO2 sequestration and enhanced oil recovery. Until recently, formation of these emulsions required stabilization with fluorinated surfactants, which are expensive and often not environmentally friendly. In this work we overcame this severe limitation by developing a fundamental understanding of the properties of surfactants the CO2-water interface and using this knowledge to design and characterize emulsions stabilized with either hydrocarbon-based surfactants or nanoparticle stabilizers. We also discovered a new concept of electrostatic stabilization for CO2-based emulsions and colloids. Finally, we were able to translate our earlier work on the synthesis of silicon and germanium nanocrystals and nanowires from high temperatures and pressures to lower temperatures and ambient pressure to make the chemistry much more accessible.

Full Text Available A supercriticalfluid (SF can be defined as a dense non condensable fluid. A fluid reaches the supercritical status when its temperature and pressure exceed the relevant critical temperature and pressure. At the critical point only a single phase exists which has some properties typical of liquids (density and some of gases (viscosity, compressibility, and mass diffusion coefficient. For pharmaceutical applications, the most widely used SF is carbon dioxide (more than 98% of the applications have been developed using this fluid because of its low and easily accessible critical temperature (31.2◦C and pressure (7.4MPa, non-flammability, non-toxicity and inexpensiveness. The physical and thermal properties of SCFs fall between those of the pure liquid and gas. SCFs offer liquid-like densities, gas-like viscosities, gas-like compressibility properties and higher diffusivities than liquids. The properties of SCFs, such as polarity, viscosity, and diffusivity, can be altered several-fold by varying the operating temperature and/or pressure during the process. This flexibility is enabling the use of SCFs for various applications in the food and pharmaceutical industries, with the drug delivery system design being a more recent addition.

To study the optimum parameters of the supercritical CO, fluid extraction of lotus leaves and chemical constituents of extractive matters. Supercritical CO2 fluid extraction condition was selected by uniform design. The extraction pressure, extraction temperature, extraction time were three factors in the experiment. GC-MS was applied for analyzing the extraction. The optimum condition were obtained: the extraction pressure was 26 Mpa, the extraction temperature was 40 degrees C, the extracion time was 90 minutes. The major constituent was 1H-Pyrrole-2-carboxaldehyde, 1-ethyl-in extractive matters. Uniform design can optimize the CO2 SupercriticalFluid Extraction process quickly and accuratly with satisfactory results.

Supercriticalfluid extraction(SFE)has many advantages,such as rapid mass transfer and high solubility.Metal samples can be extracted using supercriticalfluid with a small amount of complexant.So in comparison to conventional solvent extraction process,SFE minimizes the amount of secondary waste and the pollution to environment.In order to study the extraction of Pu using supercritical CO2,the

Supercriticalfluid extraction (SFE) of plutonium and americium from soil was successfully demonstrated using supercriticalfluid carbon dioxide solvent augmented with organophosphorus and beta-diketone complexants. Spiked Idaho soils were chemically and radiologically characterized, then extracted with supercriticalfluid carbon dioxide at 2,900 psi and 65°C containing varying concentrations of tributyl phosphate (TBP) and thenoyltrifluoroacetone (TTA). A single 45 minute SFE with 2.7 mol% TBP and 3.2 mol% TTA provided as much as 88% ± 6.0 extraction of americium and 69% ± 5.0 extraction of plutonium. Use of 5.3 mol% TBP with 6.8 mol% of the more acidic beta-diketone hexafluoroacetylacetone (HFA) provided 95% ± 3.0 extraction of americium and 83% ± 5.0 extraction of plutonium in a single 45 minute SFE at 3,750 psi and 95°C. Sequential chemical extraction techniques were used to chemically characterize soil partitioning of plutonium and americium in pre-SFE soil samples. Sequential chemical extraction techniques demonstrated that spiked plutonium resides primarily (76.6%) in the sesquioxide fraction with minor amounts being absorbed by the oxidizable fraction (10.6%) and residual fractions (12.8%). Post-SFE soils subjected to sequential chemical extraction characterization demonstrated that 97% of the oxidizable, 78% of the sesquioxide and 80% of the residual plutonium could be removed using SFE. These preliminary results show that SFE may be an effective solvent extraction technique for removal of actinide contaminants from soil.

A Computational Fluid Dynamics (CFD) simulation was performed on the proposed design for the Canadian SuperCritical Water Reactor (SCWR). The proposed Canadian SCWR is a 1200 MW(e) supercritical light-water cooled nuclear reactor with pressurized fuel channels. The reactor concept uses an inlet plenum that all fuel channels are attached to and an outlet header nested inside the inlet plenum. The coolant enters the inlet plenum at 350 C and exits the outlet header at 625 C. The operating pressure is approximately 26 MPa. The high pressure and high temperature outlet conditions result in a higher electric conversion efficiency as compared to existing light water reactors. In this work, CFD simulations were performed to model fluid flow and heat transfer in the inlet plenum, outlet header, and various parts of the fuel assembly. The ANSYS Fluent solver was used for simulations. Results showed that mass flow rate distribution in fuel channels varies radially and the inner channels achieve higher outlet temperatures. At the outlet header, zones with rotational flow were formed as the fluid from 336 fuel channels merged. Results also suggested that insulation of the outlet header should be considered to reduce the thermal stresses caused by the large temperature gradients.

Sequential supercriticalfluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (rhoextractable contaminants ranged from decades for 2-4-ring PAHs and hundreds of years for 5-6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.

Supercriticalfluid has advantages of rapid mass transfer and high solubility,which can extract different substance through changing the extracting temperature and pressure.So in comparison to conventional solvent extraction process,supercriticalfluid extraction do not need to pretreatment of the matrix,minimizes the amount of secondary waste,and the extraction

This review summarizes and discusses recent advances and applications of on-line supercriticalfluid extraction coupled to liquid chromatography, gas chromatography, and supercriticalfluid chromatographic techniques. Supercriticalfluids, due to their exceptional physical properties, provide unique opportunities not only during the extraction step but also in the separation process. Although supercriticalfluid extraction is especially suitable for recovery of non-polar organic compounds, this technique can also be successfully applied to the extraction of polar analytes by the aid of modifiers. Supercriticalfluid extraction process can be performed following "off-line" or "on-line" approaches and their main features are contrasted herein. Besides, the parameters affecting the supercriticalfluid extraction process are explained and a "decision tree" is for the first time presented in this review work as a guide tool for method development. The general principles (instrumental and methodological) of the different on-line couplings of supercriticalfluid extraction with chromatographic techniques are described. Advantages and shortcomings of supercriticalfluid extraction as hyphenated technique are discussed. Besides, an update of the most recent applications (from 2005 up to now) of the mentioned couplings is also presented in this review.

Subduction-zone magmatism is triggered by the addition of H2O-rich slab-derived components: aqueous fluid, hydrous partial melts, or supercriticalfluids from the subducting slab. Geochemical analyses of island arc basalts suggest two slab-derived signatures of a melt and a fluid. These two liquids unite to a supercriticalfluid under pressure and temperature conditions beyond a critical endpoint. We ascertain critical endpoints between aqueous fluids and sediment or high-Mg andesite (HMA) melts located, respectively, at 83-km and 92-km depths by using an in situ observation technique. These depths are within the mantle wedge underlying volcanic fronts, which are formed 90 to 200 km above subducting slabs. These data suggest that sediment-derived supercriticalfluids, which are fed to the mantle wedge from the subducting slab, react with mantle peridotite to form HMA supercriticalfluids. Such HMA supercriticalfluids separate into aqueous fluids and HMA melts at 92 km depth during ascent. The aqueous fluids are fluxed into the asthenospheric mantle to form arc basalts, which are locally associated with HMAs in hot subduction zones. The separated HMA melts retain their composition in limited equilibrium with the surrounding mantle. Alternatively, they equilibrate with the surrounding mantle and change the major element chemistry to basaltic composition. However, trace element signatures of sediment-derived supercriticalfluids remain more in the melt-derived magma than in the fluid-induced magma, which inherits only fluid-mobile elements from the sediment-derived supercriticalfluids. Separation of slab-derived supercriticalfluids into melts and aqueous fluids can elucidate the two slab-derived components observed in subduction zone magma chemistry. PMID:23112158

Subduction-zone magmatism is triggered by the addition of H(2)O-rich slab-derived components: aqueous fluid, hydrous partial melts, or supercriticalfluids from the subducting slab. Geochemical analyses of island arc basalts suggest two slab-derived signatures of a melt and a fluid. These two liquids unite to a supercriticalfluid under pressure and temperature conditions beyond a critical endpoint. We ascertain critical endpoints between aqueous fluids and sediment or high-Mg andesite (HMA) melts located, respectively, at 83-km and 92-km depths by using an in situ observation technique. These depths are within the mantle wedge underlying volcanic fronts, which are formed 90 to 200 km above subducting slabs. These data suggest that sediment-derived supercriticalfluids, which are fed to the mantle wedge from the subducting slab, react with mantle peridotite to form HMA supercriticalfluids. Such HMA supercriticalfluids separate into aqueous fluids and HMA melts at 92 km depth during ascent. The aqueous fluids are fluxed into the asthenospheric mantle to form arc basalts, which are locally associated with HMAs in hot subduction zones. The separated HMA melts retain their composition in limited equilibrium with the surrounding mantle. Alternatively, they equilibrate with the surrounding mantle and change the major element chemistry to basaltic composition. However, trace element signatures of sediment-derived supercriticalfluids remain more in the melt-derived magma than in the fluid-induced magma, which inherits only fluid-mobile elements from the sediment-derived supercriticalfluids. Separation of slab-derived supercriticalfluids into melts and aqueous fluids can elucidate the two slab-derived components observed in subduction zone magma chemistry.

Supercriticalfluid extraction (SFE) is an innovative, clean and environmental friendly technology with particular interest for the extraction of essential oil from plants and herbs. Supercritical CO(2) is selective, there is no associated waste treatment of a toxic solvent, and extraction times are moderate. Further, supercritical extracts were often recognized of superior quality when compared with those produced by hydro-distillation or liquid-solid extraction. This review provides a comprehensive and updated discussion of the developments and applications of SFE in the isolation of essential oils from plant matrices. SFE is normally performed with pure CO(2) or using a cosolvent; fractionation of the extract is commonly accomplished in order to isolate the volatile oil compounds from other co-extracted substances. In this review the effect of pressure, temperature and cosolvent on the extraction and fractionation procedure is discussed. Additionally, a comparison of the extraction yield and composition of the essential oil of several plants and herbs from Lamiaceae family, namely oregano, sage, thyme, rosemary, basil, marjoram and marigold, which were produced in our supercritical pilot-plant device, is presented and discussed.

Supercritical-fluids science and technology predate all the approaches that are currently established for graphene production by several decades in advanced materials design. However, it has only recently been proposed as a plausible approach for graphene processing. Since then, supercriticalfluids have emerged into contention as an alternative to existing technologies because of their scalability and versatility in processing graphene materials, which include composites, aerogels, and foams. Here, an overview is presented of such materials prepared through supercriticalfluids from an advanced materials science standpoint, with a discussion on their fundamental properties and technological applications. The benefits of supercritical-fluid processing over conventional liquid-phase processing are presented. The benefits include not only better performances for advanced applications but also environmental issues associated with the synthesis process. Nevertheless, the limitations of supercritical-fluid processing are also stressed, along with challenges that are still faced toward the achievement of the great expectations from graphene materials.

USAEC has conducted an evaluation of supercriticalfluid (SCF) technologies for their applicability to treatment of explosives, chlorinated hydrocarbons, and metals in soils, water, and/or waste sludge media. Off-specification explosives and propellants that have traditionally been open burned or openly detonated were also examined. Supercriticalfluids are substances which have been heated and compressed to above their critical temperatures and pressures and which possess unique transport and mass transfer properties. Supercriticalfluid extraction (SFE) uses the solvating properties of supercriticalfluids to extract one or more organic components from a mixture into a supercritical solvent (commonly CO2). The concentrated extract stream may then be recycled, reclaimed, or destroyed by other methods.

The volatile oil parts of frankincense (Boswellia carterii Birdw.) were extracted with supercritical carbon dioxide under constant pressure (15, 20, or 25 MPa) and fixed temperature (40, 50, or 60°C), given time (60, 90, or 120 min) aiming at the acquisition of enriched fractions containing octyl acetate, compounds of pharmaceutical interest. A mathematical model was created by Box-Behnken design, a popular template for response surface methodology, for the extraction process. The response value was characterized by synthetical score, which comprised yields accounting for 20% and content of octyl acetate for 80%. The content of octyl acetate was determined by GC. The supercriticalfluid extraction showed higher selectivity than conventional steam distillation. Supercriticalfluid-CO(2) for extracting frankincense under optimum condition was of great validity, which was also successfully verified by the pharmacological experiments.

Maximal potential migration of six antioxidants (AO) from five polypropylene (PP) formulations was determined by two supercriticalfluid extraction (SFE) procedures, both of which contained static and dynamic steps. All analytical conditions affecting the extraction were studied and optimized using Irgafos 168 as standard. SFE was more efficient as temperature and fluid density increased. During the static step in which the samples were exposed to the fluid without flux, the introduction of hexane and methanol as fluid modifiers significantly improved the extraction. Hexane appears to facilitate polymer swelling while methanol solvates the antioxidants. In the dynamic step (in which the extraction actually occurs) time is the key parameter. Extraction for 90 min results in an efficiency of around 75%. The introduction of modifiers during this step (by an HPLC-SFE procedure) did not produce any significant improvement. When SFE was carried out on all samples, extraction efficiency was around 75% except for Irganox 1010 and Hostanox O3. The large molecular volume of these antioxidants may be responsible for the considerable reduction of extraction efficiency. Particle size and shape of polymer sample were also important. The greater the surface to volume ratio the greater the extraction efficiency.

Supercriticalfluid extraction (SFE) of plant material with solvents like CO₂, propane, butane, or ethylene is a topic of growing interest. SFE allows the processing of plant material at low temperatures, hence limiting thermal degradation, and avoids the use of toxic solvents. Although today SFE is mainly used for decaffeination of coffee and tea as well as production of hop extracts on a large scale, there is also a growing interest in this extraction method for other industrial applications operating at different scales. In this review we update the literature data on SFE technology, with particular reference to flavors and fragrance, by comparing traditional extraction techniques of some industrial medicinal and aromatic crops with SFE. Moreover, we describe the biological activity of SFE extracts by describing their insecticidal, acaricidal, antimycotic, antimicrobial, cytotoxic and antioxidant properties. Finally, we discuss the process modelling, mass-transfer mechanisms, kinetics parameters and thermodynamic by giving an overview of SFE potential in the flavors and fragrances arena.

Full Text Available Whey protein, a by-product from cheese-making, is often used in a variety of food formulations due to its unsurpassednutritional quality and inherent functional properties. However, the possibilities for the improvement and upgrading of wheyprotein utilization still need to be explored. Reactive supercriticalfluid extrusion (SCFX is a novel technique that has beenrecently reported to successfully functionalize commercially available whey proteins into a product with enhanced functionalproperties. The specific goal of this review is to provide fundamental understanding of the reinforcement mechanism andprocessing of protein functionalization by reactive SCFX process. The superimposed extrusion variables and their interactionmechanism affect the physico-chemical properties of whey proteins. By understanding the structure, functional properties andprocessing relationships of such materials, the rational design criteria for novel functionalized proteins could be developedand effectively utilized in food systems.

Usually, elution gradient high performance liquid chromatography using polymeric octadecyl bonded phases is chosen for this kind of separation. Due to the properties of carbon dioxide, low viscosity, high eluting power, separations obtained by supercriticalfluid chromatography (SFC) are generally faster than by liquid solvents. This paper reports the study of the PAH separation by SFC. The effects of the nature and percentage of modifiers, pressure, temperature and the choice of the stationary phase (mono or poly-functional, high or low bonded density) are discussed. Results show that coupling two different columns is needed to reach the complete separation of the 16 PAHs requires by the standard of the Environmental Protection Agency (EPA 610). The separation is achieved in 25 minutes with a linear acetonitrile/CO{sub 2} mobile phase gradient. Applied to the analysis of soil extracts, this analytical technique is enable to separate numerous other compounds than standard PAHs. (author) 17 refs.

This comprehensive supercriticalfluid extraction (SFE) literature review is divided into three major sections. The first section describes the electronic literature search details including the abstract service used and the different topics searched. This section also contains an overview of the seven search topics that yielded relevant references along with a brief synopsis of the most significant literature citations. These seven groupings are (1) chemical warfare agents; (2) explosives; (3) hazardous chemicals; (4) poisons, toxins and mycotoxins; (5) toxic (lethal) chemical and toxicants; (6) pesticides in soil; and (7) pesticides from plant and animal tissues. The second section contains tables of each of these groupings. Each of the seven tables contains entries for individual literature citations listed along with the specific compounds or compound classes that are addressed. The third section refers to the abstracts used in the literature search.

Particle formation with supercriticalfluids is a promising alternative to conventional precipitation processes as it allows the reduction of particle size and control of morphology and particle size distribution without degradation or contamination of the product. The book comprehensively examines the current status of research and development and provides perspectives and insights on promising future directions. The introduction to high pressure and high temperature phase equilibria and nucleation phenomena provides the basic principles of the underlying physical and chemical phenomena, allowing the reader an understanding of the relationship between process conditions and particle characteristics. Bridging the gap between theory and application, the book imparts the scientific and engineering fundamentals for innovative particle formation processes. The interdisciplinary "modus operandi" will encourage cooperation between scientists and researchers from different but complementary disciplines. Focuses on ...

Full Text Available Aim. The aim was to evaluate the supercritical carbon dioxide extraction method with and without the addition of co-solvent to the system (mixture water: ethanol to obtain the glycosides from leaves of Stevia rebaudiana Bertoni. Methods. A SFT-150 SFE / SFR model with CO2 as a fluid was used for the supercritical extraction. The variables studied were temperature, pressure, extraction time and the presence or absence of the co-solvent (water-ethanol mixture in a concentration of 70:30 v/v, incorporated in different proportions to determine the effect on yield. The amount of glycoside sweeteners was analyzed by High Performance Liquid Chromatography (HPLC. Results. The pressure was the factor that favored the extraction, which was selective in obtaining Rebaudioside A with yields no greater than 2%. The inclusion of the co-solvent achieved an increase in yield to values of 2.9% Conclusion. Supercritical CO2 individually and mixed with ethanol-water as a co-solvent was not efficient to extract Stevia rebaudiana stevioside sweeteners

Solubility measurements of candidate coating materials have been performed in supercritical (SC) CO(2) so as to select appropriate coating materials for implementation of a solvent-free coating process previously described. Solubility of lipidic compounds such as waxes (paraffin, beeswax, Carnauba wax), pure triglycerides (tricaprin, trimyristin, tripalmitin, tristearin) and mixture of glycerides and fatty acid esters (Gelucire) in SC CO(2) were evaluated in a static mode under different temperature and pressure conditions, ranging from 13-52 degrees C and from 50-220 bar, whether the CO(2)was in its liquid or SC state. It was shown that the compounds which are mixtures of various components give rise to a selective extraction of the lower melting point components, as evidenced from thermal analysis of soluble and insoluble fractions of the coating materials.

Preliminary results are reported for the extraction and catalytic hydrocracking of Alberta bitumen and oil sands using supercriticalfluid mixtures; high levels of extraction and upgrading were attained using reaction conditions significantly milder than those previously reported.

Supercriticalfluids near the critical point are characterized by liquid-like densities and gas-like transport properties. These features are purposely exploited in different contexts ranging from natural products extraction/fractionation to aerospace propulsion. Large part of studies concerns this last context, focusing on the dynamics of supercriticalfluids at high Mach number where compressibility and thermodynamics strictly interact. Despite the widespread use also at low Mach number, the turbulent mixing properties of slightly supercriticalfluids have still not investigated in detail in this regime. This topic is addressed here by dealing with Direct Numerical Simulations (DNS) of a coaxial jet of a slightly supercritical Van der Waals fluid. Since acoustic effects are irrelevant in the Low Mach number conditions found in many industrial applications, the numerical model is based on a suitable low-Mach number expansion of the governing equation. According to experimental observations, the weakly superc...

Highlights: • The Algebraic Heat Flux Model is considered for modelling the turbulence heat flux. • A relation based on AHFM for determining Pr{sub tur} is proposed. • Results are compared with heat transfer to supercriticalfluids experimental data. - Abstract: The paper discusses capabilities and limitations of Algebraic Heat Flux Models in predicting heat transfer to supercriticalfluids. The model was implemented in a commercial code and used as a basis for obtaining an advanced definition of the turbulent Prandtl number and an improved estimate of the buoyancy production of turbulence kinetic energy. A comparison between the obtained results and experimental data available in literature is performed highlighting promising features, in particular when dealing with trans-pseudo-critical conditions. Experimental conditions using different fluids where analysed showing improvements with respect to two-equation turbulence models; a reference DNS calculation is considered as well for comparison. Calculated wall temperature values are in general well reproduced by the methodology and sensitivity analyses show that improvements may be obtained in future works by selecting case-specific AHFM parameters in association with different turbulence models.

Microalgae contain valuable biologically active lipophilic substances such as omega-3 fatty acids and carotenoids. In contrast to the recovery of vegetable oils from seeds, where the extraction with supercritical CO₂ is used as a mild and selective method, economically viable application of this method on similarly soluble oils from microalgae requires, in most cases, much higher pressure. This paper presents and verifies hypothesis that this difference is caused by high adsorption capacity of microalgae. Under the pressures usually applied in supercriticalfluid extraction from plants, microalgae bind a large fraction of the extracted oil, while under extremely high CO₂ pressures their adsorption capacity diminishes and the extraction rate depends on oil solubility in supercritical CO₂. A mathematical model for the extraction from microalgae was derived and applied to literature data on the extraction kinetics in order to determine model parameters.

Full Text Available Microalgae contain valuable biologically active lipophilic substances such as omega-3 fatty acids and carotenoids. In contrast to the recovery of vegetable oils from seeds, where the extraction with supercritical CO2 is used as a mild and selective method, economically viable application of this method on similarly soluble oils from microalgae requires, in most cases, much higher pressure. This paper presents and verifies hypothesis that this difference is caused by high adsorption capacity of microalgae. Under the pressures usually applied in supercriticalfluid extraction from plants, microalgae bind a large fraction of the extracted oil, while under extremely high CO2 pressures their adsorption capacity diminishes and the extraction rate depends on oil solubility in supercritical CO2. A mathematical model for the extraction from microalgae was derived and applied to literature data on the extraction kinetics in order to determine model parameters.

The concept of peak fidelity was shown to be helpful in modeling tubing and detector cell dimensions. Connection tubing and flow cell variances were modeled to determine appropriate internal ID's, lengths, and volumes. A low dispersion plumbing configuration, based on these calculations, was assembled to replace the standard plumbing and produced the reported results. The modifications made were straightforward using commercially available parts. The full theoretical efficiency of a 3×100 mm column packed with 1.8 μm totally porous particles was achieved for the first time in supercriticalfluid chromatography (SFC). Peak fidelity of >0.95 was maintained to below k=2. A reduced plate height as low as 1.87 was measured. Thus, true "ultra high performance" SFC was achieved, with the results a major improvement from all previous SFC reports. Since there were no efficiency losses, none could be attributed to thermal gradients caused by the expansion of the fluid over large pressure drops, under the conditions used. Similarly, changes in diffusion coefficients caused by significant decreases in density during expansion are apparently balanced by the increase in linear velocity, keeping the ratio between the diffusion coefficient and the linear velocity a constant. Changing modifier concentration to change retention was shown to not be a significant problem. All these issues have been a concern in the past. Diffusion coefficients, and viscosity data needs to be collected at high pressures before the actual limits of SFC can be discovered.

Sub-2-microns particles employed as supporting phases are known to favor column efficiency. Recently a set of columns based on sub-2-microns particles for use with supercriticalfluid mobile phases have been introduced by Waters. Five different stationary phase chemistries are available: BEH silica, BEHEthyl-pyridine, X Select CSH Fluorophenyl, HSS C18 SB and BEH Shield RP18. This paper describes the characterization of 15 stationary phases, the five different chemistries, and three particle sizes, 1.7 (or 1.8), 3.5 and 5 microns, with the same carbon dioxide–methanol mobile phase and a set of more than a hundred compounds. The interactions established in the 15 different chromatographic systems used in supercriticalfluid chromatography (SFC) are assessed with linear solvation energy relationships (LSERs).The results show the good complementarity of the five column chemistries, and their comparative location inside a classification map containing today around 70 different commercial phases. Among the five different chemistries, the HSS C18 SB phase displays a rather unusual behavior in regards of classical C18 phases, as it displays significant hydrogen–bonding interactions. Besides, it appears, as expected, that the BEH Ethyl–pyridine phase has weak interactions with basic compounds. The effect of particle size was studied because smaller particles induce increased inlet and internal pressure. For compressible fluids,this pressure change modifies the fluid density, i.e. the apparent void volume and the eluting strength.These changes could modify the retention and the selectivity of compounds in the case of method trans-fer, by using different particle sizes, from 5 down to 1.7 m. A hierarchical cluster analysis shows that stationary phase clusters were based on the phase chemistry rather than on the particle size, meaning that method transfer from 5 to 1.7 microns can be achieved in the subcritical domain i.e. by using a weakly compressible fluid.

Full Text Available Under the chromatographic point of view, the physico-chemical properties of a supercriticalfluid are intermediate to those of the gases and liquids. Many times they approach the best features of each one, as for example, the solubilization power of liquids and low viscosity of gases. The thermodynamic definitions and main physico-chemical features of a supercriticalfluid will be presented in this article. The use of supercriticalfluids in analytical chemistry has been extremely modest in Brazil, even considering the enormous potential of their applications, and their use in several techniques, such as chromatography (SFC and supercriticalfluid extration (SFE. This article series is intended to discuss the historical evolution, instrumentation features and potential and limitations of the supercriticalfluid use in analytical chemistry. A special focus will be centered on chromatography and extration techniques using supercriticalfluids.

The main objective of this research is to develop an equation of state that can be used to predict solubilities and tailor supercriticalfluid solvents for the extraction and processing of coal. To meet this objective we have implemented a two-sided. approach. First, we expanded the database of model coal compound solubilities in higher temperature fluids, polar fluids, and fluid mixtures systems. Second, the unique solute/solute, solute/cosolvent and solute/solvent intermolecular interactions in supercriticalfluid solutions were investigated using spectroscopic techniques. These results increased our understanding of the molecular phenomena that affect solubility in supercriticalfluids and were significant in the development of an equation of state that accurately reflects the true molecular makeup of the solution. (VC)

The cleaning ability of supercritical CO{sub 2} was examined on chip resistors. Extraction analyses were made by atomic absorption spectroscopy and the extent of surface cleaning observed by scanning electron microscopy. Experimental results showed that the flow-cleaning process of supercritical CO{sub 2} possessed the advantages of having a superior cleaning ability and permitting a nondrying step. These characteristics strongly suggest that supercritical CO{sub 2} is a superior alternative to the traditional deionized water used in rinsing chip resistors. Moreover, a higher pressure and temperature can benefit the cleaning ability of this novel supercritical CO{sub 2} cleaning technique.

The present study focuses on the modeling and simulation of injection, mixing, and combustion of real fluids at supercritical conditions. The objectives of the study are: (1) to establish a unified theoretical framework that can be used to study the turbulent combustion of real fluids; (2) to implement the theoretical framework and conduct numerical studies with the aim of improving the understanding of the flow and combustion dynamics at conditions representative of contemporary liquid-propellant rocket engine operation; (3) to identify the key design parameters and the flow variables which dictate the dynamics characteristics of swirl- and shear- coaxial injectors. The theoretical and numerical framework is validated by simulating the Sandia Flame D. The calculated axial and radial profiles of velocity, temperature, and mass fractions of major species are in reasonably good agreement with the experimental measurements. The conditionally averaged mass fraction profiles agree very well with the experimental results at different axial locations. The validated model is first employed to examine the flow dynamics of liquid oxygen in a pressure swirl injector at supercritical conditions. Emphasis is placed on analyzing the effects of external excitations on the dynamic response of the injector. The high-frequency fluctuations do not significantly affect the flow field as they are dissipated shortly after being introduced into the flow. However, the lower-frequency fluctuations are amplified by the flow. As a result, the film thickness and the spreading angle at the nozzle exit fluctuate strongly for low-frequency external excitations. The combustion of gaseous oxygen/gaseous hydrogen in a high-pressure combustion chamber for a shear coaxial injector is simulated to assess the accuracy and the credibility of the computer program when applied to a sub-scale model of a combustor. The predicted heat flux profile is compared with the experimental and numerical studies. The

The potential application of capillary column supercriticalfluid chromatography (SFC) and SFC/mass spectrometry (SFC/MS) for the separation and analysis of mycotoxins of the trichothecene group was examined. Trichothecenes present significant analytical problems for both gas and liquid chromatography with a major difficulty for the latter being the lack of sufficiently sensitive and selective detectors. Supercritical carbon dioxide mobile phases at temperatures up to 100 degrees C were used with deactivated fused silica columns coated with crosslinked stationary phases. Separations were obtained under pressure ramped conditions using long (15 m) 50-micron i.d. columns for several trichothecenes (diacetoxyscirpenol, deoxynivalenol, and T-2 toxin) and related higher molecular weight macrocyclic (roridin and verrucarin) trichothecenes. In addition, new rapid pressure programming techniques with short (less than 2m) 25- to 50-micron i.d. capillary columns were used to obtain fast separations in as little as 1 min. SFC/MS with ammonia chemical ionization provided high selectivity and sensitive detection (with approximately 1-pg detection limits) for trichothecene mixtures. The extension to complex sample matrices is discussed and the application of selective MS/MS detection is demonstrated.

A new chiral melatoninergic ligand, potentially successor of Valdoxan(®), presenting an improved pharmacological profile with regard to agomelatine, was chosen as a probe for a supercriticalfluid chromatographic separation carried-out on an amylose tris[(S)-1-α-methylbenzylcarbamate] based stationary phase. The goal of this work was to optimize simultaneously three factors identified to have a significant influence to obtain the best resolution in the shortest analysis time (i.e., retention time of the second eluting enantiomer) for this chiral compound. For this purpose a central circumscribed composite (CCC) design was developed with three factors: the flow-rate, the pressure outlet and the percentage of ethanol to optimize of two responses: shortest analysis time and best resolution. The optimal conditions obtained via the optimizer mode of the software (using the Nelder-Mead method) i.e., CO2/EtOH 86:14 (v:v), 104bar, 3.2mLmin(-1) at 35°C lead to a resolution of 3.27 in less than 6min. These conditions were transposed to a preparative scale where a concentrated methanolic solution of 40mM was injected with a sample loop of 100μL. This step allowed to separate an amount of around 65mg of racemic melatonin ligand in only 3h with impressive yields (97%) and enantiomeric excess (99.5%).

Full Text Available Supercriticalfluid extraction (SFE of plant material with solvents like CO2, propane, butane, or ethylene is a topic of growing interest. SFE allows the processing of plant material at low temperatures, hence limiting thermal degradation, and avoids the use of toxic solvents. Although today SFE is mainly used for decaffeination of coffee and tea as well as production of hop extracts on a large scale, there is also a growing interest in this extraction method for other industrial applications operating at different scales. In this review we update the literature data on SFE technology, with particular reference to flavors and fragrance, by comparing traditional extraction techniques of some industrial medicinal and aromatic crops with SFE. Moreover, we describe the biological activity of SFE extracts by describing their insecticidal, acaricidal, antimycotic, antimicrobial, cytotoxic and antioxidant properties. Finally, we discuss the process modelling, mass-transfer mechanisms, kinetics parameters and thermodynamic by giving an overview of SFE potential in the flavors and fragrances arena.

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercriticalfluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. The solvent is vaporized and pumped away. Solution pressure is varied to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solution temperature is varied in relation to formation of a two-phase system during expansion to control porosity of the film or powder. A wide variety of film textures and powder shapes are produced of both organic and inorganic compounds. Films are produced with regular textural feature dimensions of 1.0-2.0 .mu.m down to a range of 0.01 to 0.1 .mu.m. Powders are formed in very narrow size distributions, with average sizes in the range of 0.02 to 5 .mu.m.

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercriticalfluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. Upon expansion and supersonic interaction with background gases in the low pressure region, any clusters of solvent are broken up and the solvent is vaporized and pumped away. Solute concentration in the solution is varied primarily by varying solution pressure to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solvent clustering and solute nucleation are controlled by manipulating the rate of expansion of the solution and the pressure of the lower pressure region. Solution and low pressure region temperatures are also controlled.

Supercriticalfluid extraction (SFE), with carbon dioxide as the solvent, was tested for its ability to remove common reactive impurities from several pharmaceutical excipient powders including starch, microcrystalline cellulose (MCC), hydroxypropylcellulose (HPC), polyethylene oxide (PEO), and polyvinylpyrrolidone (PVP). Extraction of the small molecule impurities, formic acid and formaldehyde, was conducted using SFE methods under conditions that did not result in visible physical changes to polymeric excipient powders. It could be shown that spiked, largely surface-bound, impurities could be removed effectively; however, SFE could only remove embedded impurities in the excipient particles after significant exposure times due to slow diffusion of the impurities to the particle surfaces. Attempts at hydrogen peroxide extraction were hindered by its low solubility in CO2, thereby effectively precluding SFE for removal of hydrogen peroxide from excipients. This work suggests that SFE will only be commercially useful for removal of low molecular weight impurities in polymeric excipients when migration of the impurities to the particle surfaces is sufficiently rapid for extraction to be completed in a reasonable time frame.

Tomato seeds and skins acquired from the byproduct of a local tomato processing facility were studied for supercriticalfluid extraction (SFE) of phytochemicals. The extracts were analyzed for lycopene, beta-carotene, alpha-carotene, alpha-tocopherol, gamma-tocopherol, and delta-tocopherol content using high-performance liquid chromatography-electrochemical detection and compared to a chemically extracted control. SFEs were carried out using CO(2) at seven temperatures (32-86 degrees C) and six pressures (13.78-48.26 MPa). The effect of CO(2) flow rate and volume also was investigated. The results indicated that the percentage of lycopene extracted increased with elevated temperature and pressure until a maximum recovery of 38.8% was reached at 86 degrees C and 34.47 MPa, after which the amount of lycopene extracted decreased. Conditions for the optimum extraction of lycopene from 3 g of raw material were determined to be 86 degrees C, 34.47 MPa, and 500 mL of CO(2) at a flow rate of 2.5 mL/min. These conditions resulted in the extraction of 61.0% of the lycopene (7.19 microg lycopene/g).

Recent developments in biodegradable particle formation using supercriticalfluids and dense gases have been reviewed with an emphasis on studies of micronizing and encapsulating poorly-soluble pharmaceuticals and gene. General review articles published in previous years have then been provided. A brief description of the operating principles of some types of particle formation processes is given. These include the rapid expansion of supercritical solutions (RESS), the particles from gas-saturated solution (PGSS) processes, the gas antisolvent process (GAS), and the supercritical antisolvent process (SAS). The papers have been reviewed under two groups, one involving the production of particles from pure biodegradable substances, and the other involving coating, capsule, and impregnation that contain active components, especially those that relate to pharmaceuticals. This review is a comprehensive review specifically focused on the formation of biodegradable particles for drug and gene delivery system using supercriticalfluid and dense gas.

A supercriticalfluid extract of rosemary has been fractionated under supercritical conditions by using a preparative-SFC system. In this work, the optimum conditions have been evaluated to achieve a selective isolation of the compounds responsible for both, antioxidant and antimicrobial activities. A 25 cm x 10 mm i.d. LC-Diol packed column (dp=5 microm) has been used and the separation took place at 80 degrees C of column temperature, 130 bar of pressure, and 10% of ethanol as modifier of the mobile phase (CO(2)). Two cyclones were employed to collect the fractions which were subsequently characterized by HPLC-DAD, GC, and in vitro antioxidant and antimicrobial assays. By a careful selection of the separation conditions it is possible to obtain two different fractions, one enriched with antioxidant and antimicrobial compounds (with an improvement of about 20% and 40% of antioxidant and antimicrobial activity, respectively, compared to the original extract) collected in cyclone 2 and with no residual rosemary aroma and another one containing the essential oil.

Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc -CO2) system was designed to mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc -CO2 and are capable of extracting uranium directly from UO2, UO3 and U3O8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO3 loaded Sc-CO2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercriticalfluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc -CO2 pressure and temperature, TBP/HNO3 complex used

Supercriticalfluid extraction was coupled with solid-phase extraction using octadecylsilane cartridges for the selective isolation of ultratrace levels of a drug metabolite, mebeverine alcohol, from plasma. Plasma was directly applied to the extraction cartridge, the cartridge was washed to remove protein and then extracted under supercritical conditions using CO2/5% methanol. The effluent from the extraction cell was bubbled through a small volume of 2-propanol to trap the extracted mebeverine alcohol. The effects of extraction pressure and temperature on analyte recovery were examined. The absolute recovery, selectivity, precision, and accuracy of the combined supercriticalfluid extraction/solid-phase extraction approach were compared to those of conventional solid-phase extraction using gas chromatography/mass spectrometry in the selected-ion monitoring mode. Mebeverine alcohol was used as a model compound, and dog plasma was employed as the biological matrix for these studies.

Nine amide derivatives bearing α-stereocenters as well as different substitutions on the amide nitrogen were synthesized via an n-propanephosphonic acid cyclic anhydride (T3P)-mediated coupling, and their enantiomeric pairs were separated using supercriticalfluid chromatography (SFC). Five polysaccharide-based chiral stationary phases (CSPs), Chiralcel OD-H, and OJ-H, and Chiralpak AD-H, AS-H and IC columns were explored for the chiral separation of these compounds. None of the compounds could be resolved on all five columns, and no single column could separate all nine pairs of enantiomers. Comparatively, the IC and OD-H columns showed the best results for this group of amides, yielding baseline separations for eight of nine pairs. The type of polar functional group and aromatic substitution in the CSPs and the substitutions on the amide nitrogen had a significant impact on the enantiomeric resolution of the compounds in the interaction between the analyte and the stationary phases. The potential separation mechanism and the effect of substitutions in the CSPs and amide solutes on the separation are discussed. The effects of the organic modifiers, modifier composition, mobile phase additives, and temperature were investigated for the separation of these amides on the IC or the OD-H column. Baseline resolution was achieved under optimized chromatographic conditions using an IC or an OD-H column. Linearity, reproducibility, and limit of quantitation were also demonstrated for the compound 9. Approximately three-fold improvement in signal-to-noise was observed using a SFC system with better instrument design.

A reproducible and selective method was developed for the analysis of three anti-pschycotics, i.e. haloperidol, trifluoperazine and trihexyphenidyl in bulk and dosage forms using packed column supercriticalfluid chromatography (SFC). The analytes were resolved by elution with supercriticalfluid carbon dioxide doped with 16.67% (v/v) methanol containing 0.8% isopropylamine. Parallel studies were performed by HPLC using ion pairing reagent and a comparison is discussed. The method was successfully used for the assay of three formulations containing a combination of: (1) haloperidol-trihexyphenidyl; (2) haloperidol-trifluoperazine; (3) trifluoperazine-trihexyphenidyl.

Supercriticalfluids have become a hot topic in recent years, due to their wide applications in chemical and energy systems. With its sensitive thermal-transport properties in the near-critical region, supercritical/near-critical fluids behaviors, under both microgravity and terrestrial conditions, have become very interesting and challenging topic. This brief review is focused on the visualization experiments of fluid convection and heat transfer related critical phenomena by interferometer. Due to the sensitive property changes of critical fluids, it is very difficult to control and measure the supercriticalfluid behaviors. In this review, non-intrusive visualization systems by interferometry are introduced and analyzed for experimental studies of fluids in the near-critical region. For near-critical and supercritical experiments, the temperature/density control and parameter analysis are of critical importance. The analysis of boundary conditions, convection behaviors and energy transfer modes of critical fluids, mainly under weightlessness, are also reviewed with recent opinions toward future development. It is hoped that this review could be helpful for related studies.

An optimisation procedure for the supercriticalfluid extraction (SFE) of cocaine from the leaves of Erythroxylum coca var. coca was investigated by means of experimental design. After preliminary experiments where the SFE rate-controlling mechanism was determined, a central composite design was applied to evaluate interactions between selected SFE factors such as pressure, temperature, nature and percentage of the polar modifier, as well as to optimise these factors. Predicted and experimental contents of cocaine were compared and robustness of the extraction method estimated by drawing response surfaces. The analysis of cocaine in crude extracts was carried out by capillary GC equipped with a flame ionisation detector (GC-FID), as well as by capillary GC coupled with a mass spectrometer (GC-MS) for peak identification.

The application of supercriticalfluid on separation techniques and its problems are reviewed. The application is at a standstill contrary to large expectation for it except component extraction from natural foods such as caffeine removal from coffee. Various problems are thus pointed out to be solved as follows; a study on new applications other than substitutional use for organic solvents, cost reduction, a study on new safe advanced fluids suitable for specific objects other than CO2, and combination with other several separation techniques. The new practical applications of supercriticalfluid expected in the near future are as follows; low-cost mass production of antibodies by use of the immunity system of hens, drying of porous bodies intercalated in aqueous solution, removal of residual unreacted monomers and organic solvents from medical polymers, development of supercritical chromatographic equipment possible to separate pure functional food materials, and analytical extraction of functional groups including hetero atoms from harmful substances. 6 refs., 2 figs., 2 tabs.

Present study reports the development and validation of a simultaneous estimation of metformin and gliclazide in human plasma using supercriticalfluid chromatography followed by tandem mass spectrometry. Acetonitrile:water (80:20) mixture was used as a mobile phase along with liquid CO2 in supercriticalfluid chromatography and phenformin as an internal standard. The modified plasma samples were analyzed by electro-spray ionization method in selective reaction monitoring mode in tandem mass spectrometry. Supercriticalfluid chromatographic separation was performed using nucleosil C18 containing column as a stationary phase. The separated products were identified by characteristic peaks and specific fragments peaks in tandem mass spectrometry as m/z 130 to 86 for metformin, m/z 324 to 110 for gliclazide and m/z 206 to 105 for phenformin. The present method was found linear in the concentration ranges of 6.0-3550 ng/ml and 7.5-7500 ng/ml for metformin and gliclazide, respectively. Pharmacokinetic study was performed after an oral administration of dispersible tablets containing 500 mg of metformin and 80 mg of gliclazide using same techniques. PMID:20582190

The analysis of the organic pollutant in the environment is carried out as the following procedure; the organic substance is extracted by using the organic solvent from a collected sample, an instrument analysis such as gas chromatography (GC) or high performance liquid chromatography (HPLC) are done after the clean up the sample by column chromatography. The analysis using supercriticalfluid instead of the organic solvent in each stage is supercriticalfluid extraction (SFE) or supercriticalfluid chromatography (SFC). The supercriticalfluid has a density and viscosity coefficient between gas and liquid, and the control of the dissolving power is possible by the change of temperature and pressure. Therefore, it has the advantage as follows: The material mobile speed is high and separation and extraction are rapid; It is easy to adjust the dissolving power and possible to carry out selective separation and extraction; The removal of solvent can be easily carried out since supercritical CO{sub 2} used is a gas in the normal pressure. In this paper, the analytical instrument in which the extraction is carried out in organic solvent and clean up was done in SFC was introduced. (NEDO)

A number of studies have been reported on the applications of supercriticalfluids to polymeric processes. The presence of volatiles can affect the end-use properties of polymer materials. Therefore, these volatiles must be reduced to a level below the maximum permissible limit. Conventional heat-relevant techniques for polymer devolatilization sometimes have limited effectiveness. Devolatilization with supercriticalfluids, however, can enhance removal of volatiles from polymers. A model for diffusion-limited extraction is used to characterize dynamic supercriticalfluid devolatilization of spherical polymer particles. The rate of supercriticalfluid devolailization for respectively. The model analysis, which is consistent with experimental results, indicates that the supercriticalfluid devolatilization is not solubility-limited but diffusion-limited when CO2 flow rate is above 4.00 L·min-1.

Full Text Available We have developed a method of forming platinum (Pt nanoparticles using a metal organic chemical fluid deposition (MOCFD process employing a supercriticalfluid (SCF, and have demonstrated the synthesis of dispersed Pt nanoparticles on the surfaces of carbon nanowalls (CNWs, two-dimensional carbon nanostructures, and carbon nanotubes (CNTs. By using SCF-MOCFD with supercritical carbon dioxide as a solvent of metal-organic compounds, highly dispersed Pt nanoparticles of 2 nm diameter were deposited on the entire surface of CNWs and CNTs. The SCF-MOCFD process proved to be effective for the synthesis of Pt nanoparticles on the entire surface of intricate carbon nanostructures with narrow interspaces.

Full Text Available The paper presents a literature review on the topic of vapour power plants working according to the two-phase thermodynamic cycle with supercritical parameters. The main attention was focused on a review of articles and papers on the vapour power plants working using organic circulation fluids powered with low- and medium-temperature heat sources. Power plants with water-steam cycle supplied with a high-temperature sources have also been shown, however, it has been done mainly to show fundamental differences in the efficiency of the power plant and applications of organic and water-steam cycles. Based on a review of available literature references a comparative analysis of the parameters generated by power plants was conducted, depending on the working fluid used, the type and parameters of the heat source, with particular attention to the needs of power plant internal load.

The production of integrated circuits involves a number of discrete steps that utilize hazardous or regulated solvents. Environmental, safety and health considerations associated with these chemicals have prompted a search for alternative, more environmentally benign, solvent systems. An emerging technology for conventional solvent replacement is the use of supercriticalfluids based on carbon dioxide (CO{sub 2}). Supercritical CO{sub 2} (SCCO{sub 2}) is an excellent choice for IC manufacturing processes since it is non-toxic, non-flammable, inexpensive, and is compatible with all substrate and metallizations systems. Also, conditions of temperature and pressure needed to achieve the supercritical state are easily achievable with existing process equipment. The authors first describe the general properties of supercriticalfluids, with particular emphasis on their application as alternative solvents. Next, they review some of the work which has been published involving the use of supercriticalfluids, and particularly CO{sub 2}, as they may be applied to the various steps of IC manufacture, including wafer cleaning, thin film deposition, etching, photoresist stripping, and waste treatment. Next, they describe the research work conducted at Los Alamos, on behalf of Hewlett-Packard, on the use of SCCO{sub 2} in a specific step of the IC manufacturing process: the stripping of hard-baked photoresist.

The persistence, ubiquity, and toxicity of polyhalogenated compounds, together with their presence in fish feed, make it necessary to monitor these organic pollutants in the routine quality assurance programs of aquaculture activities, as this food chain is a source of these toxic compounds for human consumers. A new approach based on simultaneous supercriticalfluid extraction-sample cleanup, followed by solid-phase microextraction-gas chromatography/mass spectrometry (SFE-SPME-GC/MS/MS) has been developed as an advantageous analytical tool for the determination of 15 organohalogenated compounds (including pesticides, polychlorinated and polybrominated biphenyls, and polybrominated diphenyl ethers) in aquaculture feed at very low levels. The influence of several parameters in the efficiency of the SPE/SPME combination was systematically investigated by chemometric approaches. In the optimal conditions, the developed procedure provides an excellent linearity, detection, and quantification limits (below 10 pg/g) for most of the analytes investigated, being at the same time advantageous in terms of rapidity, convenience, and avoiding the need of toxic organic solvents. The procedure was applied to the analysis of aquaculture feed and cultured marine species and tested for accuracy against IAEA 406 reference material.

Supercritical carbon dioxide (70°C, 4,000 psi) was used to extract cedarwood oil from Eastern redcedar, Juniperus virginiana L. The CO2-derived oil was tested for biological activity against several species of arthropods, including mosquitoes, ticks, houseflies, and ants. The cedarwood oil was found...

Introduction: This report provides a detailed, step-by-step procedure for conducting extractions with supercritical carbon dioxide (CO2) using the ISCO SFX220 supercriticalfluid extraction system. Protocols for the subsequent separation and analysis of extracted hydrocarbons are also included in this report. These procedures were developed under the auspices of the project 'Assessment of Geologic Reservoirs for Carbon Dioxide Sequestration' (see http://pubs.usgs.gov/fs/fs026-03/fs026-03.pdf) to investigate possible environmental ramifications associated with CO2 storage (sequestration) in geologic reservoirs, such as deep (~1 km below land surface) coal beds. Supercritical CO2 has been used previously to extract contaminants from geologic matrices. Pressure-temperature conditions within deep coal beds may render CO2 supercritical. In this context, the ability of supercritical CO2 to extract contaminants from geologic materials may serve to mobilize noxious compounds from coal, possibly complicating storage efforts. There currently exists little information on the physicochemical interactions between supercritical CO2 and coal in this setting. The procedures described herein were developed to improve the understanding of these interactions and provide insight into the fate of CO2 and contaminants during simulated CO2 injections.

This paper presents the application of artificial neural networks (ANN) to develop new models of liquid solvent dissolution of supercriticalfluids with solutes in the presence of cosolvents. The neural network model of the liquid solvent dissolution of CO{sub 2} was built as a function of pressure, temperature, and concentrations of the solutes and cosolvents. Different experimental measurements of liquid solvent dissolution of supercriticalfluids (CO{sub 2}) with solutes in the presence of cosolvents were collected. The collected data are divided into two parts. The first part was used in building the models, and the second part was used to test and validate the developed models against the Peng- Robinson equation of state. The developed ANN models showed high accuracy, within the studied variables range, in predicting the solubility of the 2-naphthol, anthracene, and aspirin in the supercriticalfluid in the presence and absence of co-solvents compared to (EoS). Therefore, the developed ANN models could be considered as a good tool in predicting the solubility of tested solutes in supercriticalfluid.

For every 3 moles of fatty acid esters produced, 1 mole of glycerol remains, ~11% of the biodiesel volume. One new method of glycerol use could be as a biodiesel fuel additive/extender using eco-friendly heterogeneous catalysts and supercriticalfluids (SFs). SFs have advantages such as greater diff...

In this investigation, supercriticalfluid extraction (SFE) with pure CO2 was assessed as a confirmatory tool in Phase III of whole sediment toxicity identification evaluations (TIEs). The SFE procedure was assessed on two reference sediments and three contaminated sediments usi...

Valorisation of lignin plays a key role in further development of lignocellulosic biorefinery processes the production of biofuels and bio-based materials. In the present study, organosolv hardwood and wheat straw lignins were converted in a supercriticalfluid consisting of carbon dioxide/acetone/w

Various technologies pertaining to causing fluid in a supercritical Brayton cycle power generation system to flow in a desired direction at cold startup of the system are described herein. A sensor is positioned at an inlet of a turbine, wherein the sensor is configured to output sensed temperatures of fluid at the inlet of the turbine. If the sensed temperature surpasses a predefined threshold, at least one operating parameter of the power generation system is altered.

Supercriticalfluids are used in various industrial fields, such as the food and medical industries, because they have beneficial physical and chemical properties and are also nonflammable and inexpensive. In particular, supercritical carbon dioxide (ScCO(2)) is attractive due to its mild critical temperature, pressure values, and nontoxicity. Poly(L-lactide-co-ɛ-caprolactone) (PLCL), which is a biocompatible, biodegradable, and very elastic polymer, has been used in cartilage tissue engineering. However, organic solvents, such as chloroform or dichloromethane, are usually used for the fabrication of a PLCL scaffold through conventional methods. This leads to a cytotoxic effect and long processing time for removing solvents. To alleviate these problems, supercriticalfluid processing is introduced here. In this study, we fabricated a mechano-active PLCL scaffold by supercriticalfluid processing for cartilage tissue engineering, and we compared it with a scaffold made by a conventional solvent-casting method in terms of physical and biological performance. Also, to examine the optimum condition for preparing scaffolds with ScCO(2), we investigated the effects of pressure, temperature, and the depressurization rate on PLCL foaming. The PLCL scaffolds produced by supercriticalfluid processing had a homogeneously interconnected porous structure, and they exhibited a narrow pore size distribution. Also, there was no cytotoxicity of the scaffolds made with ScCO(2) compared to the scaffolds made by the solvent-pressing method. The scaffolds were seeded with chondrocytes, and they were subcutaneously implanted into nude mice for up to 4 weeks. In vivo accumulation of extracellular matrix of cell-scaffold constructs demonstrated that the PLCL scaffold made with ScCO(2) formed a mature and well-developed cartilaginous tissue compared to the PLCL scaffold formed by solvent pressing. Consequently, these results indicated that the PLCL scaffolds made by supercriticalfluid

Full Text Available The aim of this work is to present the new applications of membrane technology in fat and oil processing, with emphasis on development and applications of the enzymatic membrane reactor and its association with extraction and purification technology by supercriticalfluids (SCF. Combining the extraction by SCFs and the separation by membranes allows the integration of extractions reactions with selective separation by membranes through filtration of the supercritical mixture (SCF + extracted solutes. This association provides important energy savings regarding the SCF recompression costs.

The extraction of pepper perfume by use of supercriticalfluid extraction (SFE) was investigated. Carbon dioxide was used as supercritical mobile phase. SFE was achieved by follow conditions, temperature was 40deg C, pressure was 200 kgf/cm/sup 2/, 5 % methanol was added to mobile phase and the extraction time was 60 minutes. The extracted fraction by this method was yellow oily substance and was pepper perfume rich fraction, while the residue of extraction had not only perfume but also any pungency. And it seems that most part of pepper perfume was extracted by Supercriticalfluid extraction. The perfume fraction was analyzed by two way method, that is, supercriticalfluid chromatography (SFC) and reversed phase HPLC. SFC conditions were same as SFE. HPLC conditions were described as the first report. By both methods, about 7 peaks were detected. According to their analysis of this fraction, the main component was identified as piperine. On the chromatogram of reversed phase HPLC of extract, most peaks were eluted later than piperine. And it is thought that most perfume components have high hydrophobicity more than piperine. The change of perfume of pepper was able to be discussed based on the extraction by SFE.

Full Text Available Supercriticalfluid extraction (SFE, which has received much interest in its use and further development for industrial applications, is a method that offers some advantages over conventional methods, especially for the palm oil industry. SC-CO2 refers to supercriticalfluid extraction (SFE that uses carbon dioxide (CO2 as a solvent which is a nontoxic, inexpensive, nonflammable, and nonpolluting supercriticalfluid solvent for the extraction of natural products. Almost 100% oil can be extracted and it is regarded as safe, with organic solvent-free extracts having superior organoleptic profiles. The palm oil industry is one of the major industries in Malaysia that provides a major contribution to the national income. Malaysia is the second largest palm oil and palm kernel oil producer in the World. This paper reviews advances in applications of supercritical carbon dioxide (SC-CO2 extraction of oils from natural sources, in particular palm oil, minor constituents in palm oil, producing fractionated, refined, bleached, and deodorized palm oil, palm kernel oil and purified fatty acid fractions commendable for downstream uses as in toiletries and confectionaries.

Supercriticalfluid extraction (SFE), which has received much interest in its use and further development for industrial applications, is a method that offers some advantages over conventional methods, especially for the palm oil industry. SC-CO₂ refers to supercriticalfluid extraction (SFE) that uses carbon dioxide (CO₂) as a solvent which is a nontoxic, inexpensive, nonflammable, and nonpolluting supercriticalfluid solvent for the extraction of natural products. Almost 100% oil can be extracted and it is regarded as safe, with organic solvent-free extracts having superior organoleptic profiles. The palm oil industry is one of the major industries in Malaysia that provides a major contribution to the national income. Malaysia is the second largest palm oil and palm kernel oil producer in the World. This paper reviews advances in applications of supercritical carbon dioxide (SC-CO₂) extraction of oils from natural sources, in particular palm oil, minor constituents in palm oil, producing fractionated, refined, bleached, and deodorized palm oil, palm kernel oil and purified fatty acid fractions commendable for downstream uses as in toiletries and confectionaries.

Extensive discussion continues regarding the relative merits of capillary and packed columns for supercriticalfluid chromatography (SFC). Columns of interest typically include commercially available 50-..mu..m i.d. capillaries having an /approximately/0.25-..mu..m film thickness and packed columns containing 3-..mu..m or 5-..mu..m diameter developed for HPLC. It has been demonstrated that packed columns can offer advantages in terms of speed because the properties of fluids high linear velocities to be utilized, but the lower pressure drop with open tubular capillary columns allows a greater number of effective theoretical plates through the use of longer columns. Much discussion has centered about the comparison of columns under various operating conditions of practical interest (e.g., pressure programming for capillaries or isobaric operation for packed columns). It is the purpose of this report to show the importance of column phase ratio (i.e., the ratio of stationary to mobile phase volumes. V/sub s/ and V/sub m/, respectively in the selection of columns for specific SFC applications.

Discover the many new and emerging applications of supercritical water as a green solvent Drawing from thousands of original research articles, this book reviews and summarizes what is currently known about the properties and uses of supercritical water. In particular, it focuses on new and emerging applications of supercritical water as a green solvent, including the catalytic conversion of biomass into fuels and the oxidation of hazardous materials. Supercritical Water begins with an introduction that defines supercriticalfluids in general. It then defines supercritical wa

The identification of a suitable stationary phase in supercriticalfluid chromatography (SFC) is a major source of difficulty for those with little experience in this technique. Several protocols have been suggested for column classification in high-performance liquid chromatography (HPLC), gas chromatography (GC), and SFC. However, none of the proposed classification schemes received general acceptance. A fair way to compare columns was proposed with the sum of ranking differences (SRD). In this project, we used the retention data obtained for 86 test compounds with varied polarity and structure, analyzed on 71 different stationary phases encompassing the full range in polarity of commercial packed columns currently available to the SFC chromatographer, with a single set of mobile phase and operating conditions (carbon dioxide-methanol mobile phase, 25°C, 150bar outlet pressure, 3ml/min). First, a reference column was selected and the 70 remaining columns were ranked based on this reference column and the retention data obtained on the 86 analytes. As these analytes previously served for the calculation of linear solvation energy relationships (LSER) on the 71 columns, SRD ranks were compared to LSER methodology. Finally, an external comparison based on the analysis of 10 other analytes (UV filters) related the observed selectivity to SRD ranking. Comparison of elution orders of the UV filters to the SRD rankings is highly supportive of the adequacy of SRD methodology to select similar and dissimilar columns.

The multicomponent potential theory of adsorption (MPTA), which has been previously used to study low-pressure adsorption of subcritical fluids, is extended to adsorption equilibria from supercriticalfluids up to high pressures. The MPTA describes an adsorbed phase as an inhomogeneous fluid...... with thermodynamic properties that depend on the distance from the solid surface (or position in the porous space). The description involves the two kinds of interactions present in the adsorbed fluid, i.e. the fluid-fluid and fluid-solid interactions. accounted for by means of an equation of state (Eo......S) and interaction potential functions, respectively. This makes it possible to generate the different MPTA models by combination of the relevant EoS/potentials. In the present work, the simplified perturbed-chain statistical associating fluid theory (sPC-SAFT) EoS is used for the thermodynamic description of both...

This study introduces a new tracer that is useful for the determination of the hold-up time or volume of packed columns, particularly of those used in supercriticalfluid chromatography. The thermodynamic void volume of three columns packed with different adsorbents were determined using the weight difference method. These void volumes were used as the reference point in the further discussion. The hold-up volumes of these columns were determined under dynamic conditions, using nitrous oxide dissolved in methanol as the hold-up time marker. Changes in the hold-up volumes of these columns were monitored during changes of the volumetric flow rate of pure supercritical carbon dioxide and of dilute mixtures of organic modifier and supercritical carbon dioxide. The results suggest significant methanol enrichment on the adsorbent surface.

The Supercritical Water Reactor (SCWR) has been proposed as one of the six Generation IV reactor design concepts under consideration. The key feature of the SCWR is that water at supercritical pressures is used as the reactor coolant. At supercritical pressures, the working fluid does not undergo phase change as it is heated, but rather the fluid properties experience dramatic variations throughout what is known as the pseudo-critical region. Highly nonuniform temperature and uid property distributions are expected in the reactor core, which will have a significant impact on turbulence and heat transfer as well as stability limits for future SCWRs. The goal of this work is to understand and predict the effects of these fluid property variations on turbulence and heat transfer throughout the reactor core and to predict the potential onset of dynamic instabilities. CO2 at supercritical conditions is included in the current study due in some part to its use as a viable simulant fluid in place of water for experimental studies. The use of CO2 at supercritical conditions as a reactor coolant has also gained popularity in recent years. Spline-type property models have been developed for both water and CO2 at supercritical pressures in order to include the property variations into a numerical solver. Turbulence and heat transfer models for fluids at supercritical conditions have been developed and implemented into the NPHASE-CMFD computer code. The results of predictions using the proposed models have been compared to experimental data from the Korea Atomic Energy Research Institute (KAERI) for various heat transfer regimes. While no model is without some deficiency, the Chien Low-Reynolds k -- epsilon model performs best at predicting the experimental data. A stability model has been developed and is presented in this dissertation as well. This model utilizes three different solution methods and tests the effects of inlet temperature, mass flow rate, local loss

Liquid phase hydrogenation of phenol over Pt/C catalysts was investigated under conventional conditions and supercritical carbon dioxide (scCO2). The equivalent ration of hydrogen to phenol shows a significant effect on the product selectivity. Hydrogenation of phenol in different solvents was also studied, the experimental results show that polarity of solvents influences the yield of cyclohexanone remarkably, scCO2 has the highest one. Catalytic hydrogenation of phenol in scCO2 or sub-scCO2 was emphatically researched. The result is that near the critical point of CO2 phenol has higher reaction activity than that of normal organic solvents, cyclohexanone has 47% in yield and 87% in selectivity.

The main curing reactions of a portland cement are the formation of portlandite, Ca(OH){sub 2}, and calcium silicate hydrates, CSH. In nature, the cement extracts CO{sub 2} from air and convert the calcium hydroxide and CSH to calcium carbonate(CaCO{sub 3}), calcite. This process forms chemically stable and mechanically enhanced cement. By exposing an OPC to supercritical CO{sub 2}(SCCO2), the carbonate reaction was greatly accelerated. XRD analysis of compressive strength showed the mechanical enhancement.

The Growth and Morphology of SupercriticalFluids (GMSF) is an international experiment facilitated by the NASA Glenn Research Center and under the guidance of U.S. principal investor Professor Hegseth of the University of New Orleans and three French coinvestigators: Daniel Beysens, Yves Garrabos, and Carole Chabot. The GMSF experiments were concluded in early 1999 on the Russian space station Mir. The experiments spanned the three science themes of near-critical phase separation rates, interface dynamics in near-critical boiling, and measurement of the spectrum of density fluctuation length scales very close to the critical point. The fluids used were pure CO2 or SF6. Three of the five thermostats used could adjust the sample volume with the scheduled crew time. Such a volume adjustment enabled variable sample densities around the critical density as well as pressure steps (as distinct from the usual temperature steps) applied to the sample. The French-built ALICE II facility was used for these experiments. It allows tightly thermostated (left photograph) samples (right photograph) to be controlled and viewed/measured. Its diagnostics include interferometry, shadowgraph, high-speed pressure measurements, and microscopy. Data were logged on DAT tapes, and PCMCIA cards and were returned to Earth only after the mission was over. The ground-breaking near critical boiling experiment has yielded the most results with a paper published in Physical Review Letters (ref. 1). The boiling work also received press in Science Magazine (ref. 2). This work showed that, in very compressible near-critical two-phase pure fluids, a vapor bubble was induced to temporarily overheat during a rapid heating of the sample wall. The temperature rise in the vapor was 23-percent higher than the rise in the driving container wall. The effect is due to adiabatic compression of the vapor bubble by the rapid expansion of fluid near the boundary during heatup. Thermal diffusivity is low near the

, sulfur hexafluoride (insulating gas or their mixtures, etc. Their major characteristics include lower vapor pressure if compared with liquid СО2, antimicrobic activity allowing to solve one the main problem in phytochemical production – microbial contamination of extracts (and other herbal drug preparations, possibility to extract not only lipophilic, but also more polar substances depending on choice of solvents or their mixes and their higher extraction rate.It has been found that some kinds of freons (for example, R22 due to their higher polarity are able to take wider spectrum of BAS than liquid СО2: essential and fat oils, fat-soluble vitamins, coumarins, carotenoids, phenolic alcohols, valrates, iridoids, some alkaloids and flavonoids. Besides, certain freons (for example, С318 have very high selectivity allowing to extract essential oils without accompanying fats. Some condensed gases, such as liquid ammonia, dimethyl ether and difluoromethane (freon R32 can be used as well for obtaining of hydrophilic BAS (saponins, alkaloids, flavonoids. Thus such solvents should be polar enough or can be mixed with polar modifiers. Supercriticalfluids and some subcritical condensed gases are suitable for fractionating of primary (crude extracts because their selectivity considerably depends on temperature, pressure and composition (in case of mixtures with each other or with cosolvents. Also high selectivity of condensed gas and SCFs is shown in near-critical areas. Very important property of most of condensed gases and SCFs is their ability to considerably reduce microbial contamination of extracts in comparison with initial plant raw materials. Conclusions. Among existing methods for intensification of stage of plant extraction the most applicable for commercial scale is use of condensed gases and supercriticalfluids as extractants. It is found that for today in the world the most widespread SCF is carbon dioxide. The main lacks of СО2 as an extractant are high

Objectives for this quarter were to attempt to develop a model to predict the molecular diffusion coefficients to a high degree of accuracy so the authors may be able to predict both the molecular diffusion coefficient and thus the effective diffusivity a priori. They are working on a semi-empirical equation based on the rough hard sphere theory to predict diffusion coefficients in supercriticalfluids. In addition, they planned to take additional data in order to extend the database available for development of the predictive equation. The paper discusses accomplishments and problems related to the diffusion coefficients of F-T products in supercriticalfluids. Data are presented on the diffusion coefficients of 1-octene in ethane, propane, and hexane.

Supercriticalfluid extraction (SFE) is currently being investigated as a possible technique in the production of high quality mesophase pitch from coal tar and petroleum pitches. Mesophase pitch is used to make high technology products, such as carbon fibre. The conventional production of mesophase pitch initially involves the removal of low molecular weight species from coal tar and petroleum pitches. The remaining residue is then transformed into a mesophase pitch through a polym...

In this study we investigate the recently reported use of water-containing modifiers for separation and purification of hydrophilic compounds by supercriticalfluid chromatography. Improved peak shape is obtained for a variety of glycosides and otherwise hydrophilic compounds when 5% water is added to the methanol co-solvent used in SFC separations, and examples of the use of this approach in preparative SFC purifications are presented.

This paper aimed to develop a standalone application for optimizing flow rates in liquid chromatography (LC), gas chromatography (GC) and supercriticalfluid chromatography (SFC). To do so, Van Deemter’s equation, Knox’ equation and Golay’s equation were implemented in a MATLAB script and subsequently a graphical user interface (GUI) was created. The application will show the optimal flow rate or linear velocity and the corresponding plate height for the set input parameters. Furthermore, a p...

The use of supercriticalfluid carbon dioxide (SFCO2) in extraction of lanolin and its alcohol is superior to the conventional solvent extraction method. Its distinctive advantages include high extractive ratio, nontoxic and nonflammable solvents, and minimal by -product pollution. The resulting refined lanolin and its alcohol have light color and little odor, and can be used as raw materials for high grade cosmetic products.

Supercriticalfluid extraction is gaining acceptance as an alternative sample preparation method for trace organic analysis. The development of SFE instrumentation optimized for field use requires taking several technical design issues including size and weight requirements, user-friendly operation, and technical performance capabilities into consideration. Parameters associated with a prototype SFE instrument under development for potential use in conducting on-site inspections of the Chemical Weapons Convention and its preliminary technical and operational performance are described.

p. 351–355 Solubilities of several organic solids in four supercriticalfluids are calculated with Soave and Peng-Robinson equations of state, incorporating excess Gibbs free energy into the mixing rules, with Heidemann-Kokal, Wong-Sandler and MHV2 procedures. Three excess Gibbs free energy models are used in the mixing rules: NRTL, UNiQUAC and UNIFAC. Furthermore, a comparison between these mixing rules and conventional two-binary-parameter form and modification of the excluded volume par...

Supercritical carbon dioxide can be used to carry out a selective and fast extraction (30 min) of volatile hydrocarbons and 2-alkylcyclobutanones contained in irradiated foods. After elimination of the traces of triglycerides still contained in the extracts on a silica column, the compounds were ana

An interface has been developed that connects a supercriticalfluid reaction (SFR) vessel directly on-line to a liquid chromatograph. The combined SFR-LC system has enabled the progress of the esterification reaction between phenol and benzoyl chloride to synthesize phenyl benzoate in supercriticalfluid carbon dioxide solution to be dynamically monitored. This was achieved by the periodic SFR-LC analysis of samples directly withdrawn from the esterification reaction mixture. Using the series of SFR-LC analysis results obtained for individual esterification reactions, the reaction progress profile for each esterification reaction was obtained by expressing the measured yield of phenyl benzoate as a function of reaction time. With reaction temperature fixed at 75°C, four sets (n=3) of SFR-LC reaction progress profiles were obtained at four different SFR pressures ranging from 13.79 to 27.58 MPa. The maximum SFR yield obtained for phenyl benzoate using a standard set of reactant concentrations was 85.2% (R.S.D. 4.2%) when the reaction was performed at 13.79 MPa for 90 min. In comparison, a phenyl benzoate yield of less than 0.3% was obtained using the same standard reactant concentrations after 90 min reaction time at 75°C using either: heptane, ethyl acetate or acetonitrile as conventional organic reaction solvents.

A fast chromatographic separation of indole alkaloids from Evodiae fructus was developed by supercriticalfluid chromatography (SFC). The initial screening of four stationary phases was investigated with a standard mixture of evodiamine and rutaecarpine, and a complex sample of indole alkaloids prepared from Evodiae fructus as probes. Later, the effects of chromatographic parameters on separation were studied including injection volume, organic modifier, additive, temperature and back pressure. The injection volume had significant impact on the peak shape. With the additives in the mobile phase, slight changes in peak shape and retention time were observed in separation. Variation in organic modifier led to dramatic change in chromatographic behavior. Both decreased temperature and increased back pressure shortened the retention time. Finally, a fast analytical method using SFC, on a Waters ACQUITY UPC2 BEH column, methanol as modifier, under 35 degrees C and 2.07 x 10(7) Pa, was developed to separate a complex sample of indole alkaloids in less than 15 min. Another rapid approach for the separation of a complex sample of indole alkaloids was developed by using ultra-high performance liquid chromatography (UHPLC). As a result, SFC can be used in the separation of natural products, giving high performance, good resolution and fast analysis speed. The difference in selectivity with UHPLC can be used to the development of natural product separation.

The screening of plant material, the chemical composition, the abundance and the biological activity of triterpenoids are of a major economical importance. The classical analytical methods, such as TLC, GC, and HPLC are either little resolutive, or require derivatization steps, or fail in sensitivity. The supercriticalfluid chromatography/evaporative light scattering detector (SFC/ELSD) coupling provides high resolution, fast analysis and higher responses for the analysis of triterpenoids. After the initial screening of seven stationary phases to select the well suited one, analytical conditions (modifier percentage, from 10 to 3%; backpressure (from 12 to 18 MPa) and temperature (from 15 to 25 °C) were studied to improve the separation, and ELSD detection of a standard mixture composed of 8 triterpenoids (oleanolic acid, erythrodiol, β-amyrin, ursolic acid, uvaol, betulinic acid, betulin, lupeol). Applied to apple pomace extracts, this method allows the separation of about 15 triterpenoid compounds, in less than 20 min, with isocratic conditions. Moreover, the ELSD response is dramatically higher than the one provided by UV detection, and avoids derivatization steps. An attempt to identify some compounds was done by collecting chromatographic peaks and further analyzing them with mass spectrometry. Complete identification or molecular formula could be proposed for 11 compounds. However, due to the presence of position and orientation isomers the absolute identification remains difficult, despite some retention rules deduced from the standard analysis.

Eucalyptus bark contains significant amounts of triterpenoids with demonstrated bioactivity, namely triterpenic acids and their acetyl derivatives (ursolic, betulinic, oleanolic, betulonic, 3-acetylursolic, and 3-acetyloleanolic acids). In this work, the supercriticalfluid extraction (SFE) of Eucalyptus globulus deciduous bark was carried out with pure and modified carbon dioxide to recover this fraction, and the results were compared with those obtained by Soxhlet extraction with dichloromethane. The effects of pressure (100-200 bar), co-solvent (ethanol) content (0, 5 and 8% wt), and multistep operation were studied in order to evaluate the applicability of SFE for their selective and efficient production. The individual extraction curves of the main families of compounds were measured, and the extracts analyzed by GC-MS. Results pointed out the influence of pressure and the important role played by the co-solvent. Ethanol can be used with advantage, since its effect is more important than increasing pressure by several tens of bar. At 160 bar and 40 °C, the introduction of 8% (wt) of ethanol greatly improves the yield of triterpenoids more than threefold.

Full Text Available The objective of this study was to improve the dissolution and bioavailability of silymarin (SM. Solid dispersions (SDs were prepared using solution-enhanced dispersion by supercriticalfluids (SEDS and evaluated in vitro and in vivo, compared with pure SM powder. The particle sizes, stability, and contents of residual solvent of the prepared SM-SDs with SEDS and solvent evaporation (SE were investigated. Four polymer matrix materials were evaluated for the preparation of SM-SD-SEDS, and the hydrophilic polymer, polyvinyl pyrrolidone K17, was selected with a ratio of 1:5 between SM and the polymer. Physicochemical analyses using X-ray diffraction and differential scanning calorimetry indicated that SM was dispersed in SD in an amorphous state. The optimized SM-SD-SEDS showed no loss of SM after storage for 6 months and negligible residual solvent (ethanol was detected using gas chromatography. In vitro drug release was increased from the SM-SD-SEDS, as compared with pure SM powder or SM-SD-SE. In vivo, the area under the rat plasma SM concentration-time curve and the maximum plasma SM concentration were 2.4-fold and 1.9-fold higher, respectively, after oral administration of SM-SD-SEDS as compared with an aqueous SM suspension. These results illustrated the potential of using SEDS to prepare SM-SD, further improving the biopharmaceutical properties of this compound.

Stereoisomer interconversion of chiral drug substances is of significant importance if it occurs within pharmacological and pharmaceutical time scales and under physiological and shelf life conditions. Several analytical techniques exist for the determination of first order rate constants and enantiomerization energy barriers by dynamic and stopped flow chromatography, mathematical models and functions, and computer programs. The focus of this work is to utilize a simple supercriticalfluid chromatography (SFC) chiral assay to determine the possibility of interconversion of the desired R and less active S isomers of a drug candidate. The rate constants of racemization and enantiomerization, the half life of racemization, and enantiomerization energy barriers were determined for the R-->S (or, forward) and S-->R (or, reverse) conversions. The method was selective and sensitive enough to detect less than 1% interconversion occurring under the conditions studied. The method also demonstrated that R S racemization was possible only under extreme conditions of prolonged heating (80 degrees C) and highly basic pH (9.5).

The use of additives to dramatically extend the range of solute polarity amenable to CO(2) based supercriticalfluid chromatography (pcSFC) was predicted over 20 years ago. At that time additives were predicted to have multiple functions such as enhancement of mobile phase solvating power, ion suppression, and ion pairing. The adsorption of mobile phase components on the stationary phase causing a modification of its surface was predicted, but the implications for separations were not defined. Reports published in the late 1980s showed that while water could not function as a primary modifier due to it poor solubility in carbon dioxide, its use as an additive was more promising. The past decade has seen very little published work concerning water and pcSFC. Now reports are beginning to appear that demonstrate enhanced selectivity with water, and application of the technology to polypeptide salts, drug molecules, and nucleobases. This review attempts to bridge the past with the present. As evidenced by the studies described in this review, water may offer much potential as an additive in that it could (a) enhance the solvating power of the mobile phase, (b) introduce HILIC-like analyte partitioning, (c) simplify preparative purifications, and (d) offer a more mass spectrometrically compatible interface.

This study investigates the heat transfer in a simple pure fluid whose temperature is slightly above its critical temperature. We propose a efficient numerical method to predict the heat transfer in such fluids when the gravity can be neglected. The method, based on a simplified thermodynamic approach, is compared with direct numerical simulations of the Navier-Stokes and energy equations performed for CO2 and SF6. A realistic equation of state is used to describe both fluids. The proposed method agrees with the full hydrodynamic solution and provides a huge gain in computation time. The connection between the purely thermodynamic and hydrodynamic descriptions is also discussed.

Supercriticalfluid chromatography (SFC), operated in conventional mode, is normally recognized as normal phase chromatography, and uses a solvent combination of supercritical CO2 and alcohols to separate compounds. Hexane, a commonly used solvent in normal phase liquid chromatography (NP-LC), is rarely used in SFC and, in some cases, is added to the organic modifiers to increase liquid content in order to achieve better efficiency in preparative SFC for poorly retained compounds. Although hexane is believed to have similar solvent strength to that of supercritical CO2, its effects on the enantioseparation in SFC is largely unknown. To understand the chromatographic effects of an apolar solvent, such as hexane in SFC, we compared the chromatographic behaviors of 35 chiral compounds using a parallel SFC method under traditional SFC mode of only “pure” alcohol-CO2 to that of hexane-assisted SFC (HA-SFC), which uses mixtures of alcohol and hexane (as cosolvents) and CO2. We observed that, in some cases, hexane behaves just like supercritical CO2, where replacement of a portion of CO2 with hexane does not significantly change retention times or resolution of the peaks. In many cases, however, addition of hexane in mobile phases does affect chromatographic behavior of one or both enantiomers. Such effects might provide opportunities for separation of some enantiomers.

Full Text Available Triterpene compounds like betulin, betulinic acid, erythrodiol, oleanolic acid and lupeol are known for many pharmacological effects. All these substances are found in the outer bark of birch. Apart from its pharmacological effects, birch bark extract can be used to stabilise semisolid systems. Normally, birch bark extract is produced for this purpose by extraction with organic solvents. Employing supercriticalfluid technology, our aim was to develop a birch bark dry extract suitable for stabilisation of lipophilic gels with improved properties while avoiding the use of toxic solvents. With supercritical carbon dioxide, three different particle formation methods from supercritical solutions have been tested. First, particle deposition was performed from a supercritical solution in an expansion chamber. Second, the Rapid Expansion of Supercritical Solutions (RESS method was used for particle generation. Third, a modified RESS-procedure, forming the particles directly into the thereby gelated liquid, was developed. All three methods gave yields from 1% to 5.8%, depending on the techniques employed. The triterpene composition of the three extracts was comparable: all three gave more stable oleogels compared to the use of an extract obtained by organic solvent extraction. Characterizing the rheological behaviour of these gels, a faster gelling effect was seen together with a lower concentration of the extract required for the gel formation with the supercriticalfluid (SCF-extracts. This confirms the superiority of the supercriticalfluid produced extracts with regard to the oleogel forming properties.

The supercritical carbon dioxide (SCO{sub 2}) gas turbine Brayton cycle has been not only adopted in the secondary loop of the Generation IV nuclear energy systems but also planned to be installed in the high efficiency power conversion cycles of the nuclear fusion reactors. The potential beneficiaries include the Korea Advanced Liquid Metal Reactor (KALIMER), the Korea Superconducting Tokamak Advanced Research (KSTAR) as well as the International Thermonuclear Experimental Reactor (ITER). The reason for these welcomed applications is that the cycle can achieve the overall energy conversion efficiency as high as 45%. The SCO{sub 2} turbine efficiency is one of the major parameters affecting the overall Brayton cycle efficiency. Thus, optimal turbine design determines the economics of the Generation IV as well as the future nuclear fission and fusion energy industry. Seoul National University has recently been working on the SCO{sub 2} based Modular Optimized Brayton Integral System (MOBIS). MOBIS includes the Gas Advanced Turbine Operation Study (GATOS), the Loop Operating Brayton Optimization Study (LOBOS), the Nonsteady Operation Multidimensional Online Simulator (NOMOS), and the Turbine Advanced Compressor Operation Study (TACOS). This paper presents results from GATOS.

The supercritical carbon dioxide (SCO{sub 2}) gas turbine Brayton cycle has been not only adopted in the secondary loop of the Generation IV nuclear energy systems but also planned to be installed in the high efficiency power conversion cycles of the nuclear fusion reactors. The potential beneficiaries include the Korea Advanced Liquid Metal Reactor (KALIMER), Korea Superconducting Tokamak Advanced Research (KSTAR) and International Thermonuclear Experimental Reactor (ITER). The reason for these welcomed applications is that the cycle can achieve the overall energy conversion efficiency as high as 45%. The SCO{sub 2} turbine efficiency is one of the major parameters affecting the overall Brayton cycle efficiency. Thus, optimal turbine design determines the economics of the Generation IV as well as the future nuclear fission and fusion energy industry. Seoul National University has recently been working on the SCO{sub 2} based Modular Optimized Brayton Integral System (MOBIS). MOBIS includes the Gas Advanced Turbine Operation Study (GATOS), the Loop Operating Brayton Optimization Study (LOBOS), the Nonsteady Operation Multidimensional Online Simulator (NOMOS), and the Turbine Advanced Compressor Operation Study (TACOS). This paper presents first results from GATOS.

Yeast-leavened dough processing is semicontinuous due to the requirement for fermentation at constant temperature and humidity. Also, new regulations on the emission of alcohols are becoming burdensome on the baking industry. Extrusion processing of dough with supercritical carbon dioxide (SC-CO(2)) is envisioned to alleviate emission problems and to decrease production time by eliminating fermentation. A bread dough formulation with 50% (w/w) moisture was leavened by injecting 1.5% (w/w) SC-CO(2) in a twin-screw extruder at 37 degrees C. Specific mechanical energy input was 260 kJ/kg. The operating apparent shear rate range was 60-260 s(-1). SCFX-leavened dough density (420-430 kg/m(3)) was in good agreement with values reported for similar doughs. The flow behavior index, obtained by an on-line slit rheometer, was 0.49 for the nonleavened control and 0.63 for the SCFX-leavened dough. Apparent viscosity of the SCFX-leavened dough varied from 37 to 23 Pa-s. This new continuous process offers attractive possibilities for industrial applications if further developed.

The growing interest in exploiting supercritical geothermal reservoirs calls for a thorough identification and understanding of physico-chemical processes occuring in geological settings with a high heat flow. In reservoir engineering, electrical sounding methods are common geophysical exploration and monitoring tools. However, a realistic interpretation of field measurements is based on the knowledge of both, the physical properties of the rock and those of the interacting fluid at defined temperature and pressure conditions. Thus, laboratory studies at simulated in-situ conditions provide a link between the field data and the material properties in the depth. The physico-chemical properties of fluids change dramatically above the critical point, which is for pure water 374.21 °C and 221.2 bar. In supercriticalfluids mass transfer and diffusion-controlled chemical reactions are enhanced and cause mineral alterations. Also, ion mobility and ion concentration are affected by the change of physical state. All this cause changes in the electrical resistivity of supercriticalfluids and may have considerable effects on the porosity and hydraulic properties of the rocks they are in contact with. While there are some datasets available for physical and chemical properties of water and single component salt solutions above their critical points, there exist nearly no data for electrical properties of mixed brines, representing the composition of natural geothermal fluids. Also, the impact of fluid-rock interactions on the electrical properties of multicomponent fluids in a supercritical region is scarcely investigated. For a better understanding of fluid-driven processes in a near- and supercritical geological environment, in the framework of the EU-funded FP7 program IMAGE we have measured (1) the electrical resistivity of geothermal fluids and (2) physical properties of fluid saturated rock samples at simulated in-situ conditions. The permeability and electrical

The performance of a 3.0mm×150mm column packed with 1.8μm fully porous HSS-SB-C18 particles was investigated in supercriticalfluid chromatography (SFC) with low-density, highly expansible carbon dioxide. These conditions are selected for the analysis of semi-volatile compounds. Elevated temperatures (>100°C) were then combined with low column back pressures (temperature of pure carbon dioxide was set at 107°C, the active back pressure regulator (ABPR) pressure was fixed at 100bar, and the flow rate was set at 2.1mL/min at 12°C (liquefied carbon dioxide) and at an inlet column pressure close to 300bar. Nine n-alkylbenzenes (from benzene to octadecylbenzene) were injected under linear (no sample overload) conditions. The severe steepness of the temperature gradients across the column diameter were predicted from a simplified heat transfer model. Such conditions dramatically lower the column performance by affecting the symmetry of the peak shape. In order to cope with this problem, three different approaches were experimentally tested. They include (1) the decoupling and the proper selection of the inlet eluent temperature with respect to the oven temperature, (2) the partial thermal insulation of the column using polyethylene aerogel, and (3) the application of a high vacuum (10(-5)Torr provided by a turbo-molecular pump) in a housing chamber surrounding the whole column body. The results reveal that (1) the column efficiency can be maximized by properly selecting the difference between the eluent and the oven temperatures, (2) the mere wrapping of the column with an excellent insulating material is insufficient to fully eliminate heat exchanges by conduction and the undesirable radial density gradients across the column i.d., and (3) the complete thermal insulation of the SFC column under high vacuum allows to maximize the column efficiency by maintaining the integrity of the peak shape.

Owing to an environment-friendly utilization of resources, increased attention has been focused on fuels and chemicals from biomass as an alternative to fossil resources. In addition, supercriticalfluid technology has been considered to be an environmentally-benign treatment. Therefore, its technology was applied for a conversion of biomass to useful fuels and chemicals in order to mitigate environmental loading. For example, supercritical water treatment has demonstrated that lignocellulosics can be hydrolyzed to become lignin-derived products for useful aromatic chemicals and carbohydrate-derived products, such as polysaccharides,oligosaccharides and monosaccharides of glucose, mannose and xylose used for subsequent ethanol fermentation. If this treatment is prolonged, lignocellulosics were found to be converted to organic acids such as formic, acetic, glycolic and lactic acids which can be converted to methane for biofuel. When alcohols, such as methanol and ethanol, were used instead of water, some other useful products were achieved, and its liquefied products were found to have a potential for liquid biofuel. In this study, therefore, our research achievements in supercriticalfluid science of woody biomass will be introduced for clean and green chemistry for a sustainable environment.

Full Text Available Isolation, fractionation, and identification of sucrose esters from aged oriental tobacco employing supercriticalfluids have been completed. Underivatized sucrose ester-rich extracts were obtained using supercritical CO2 at densities greater than 0.73 g/mL. Lower density CO2 provided extracts with notable amounts of tobacco derived material; yet, no detectable sucrose ester content. Preparative supercriticalfluid chromatography (SFC provided for an additional purification of the sucrose ester-enriched fraction after column optimization. Structural assignments of the SFC fractions were facilitated using gas chromatography/mass spectrometry (GC/MS accompanied by N, O-bis(trimethylsilyltrifluoroacetamide-dimethylformamide (BSTFA-DMF derivatization of the free hydroxyl groups and high performance-liquid chromatography/mass spectrometry (HPLC/MS. From a relative quantitative perspective regardless of tobacco type, sucrose esters having an acetyl group on C6 of the glucose function (Group III were in higher concentration compared to both the concentration observed for sucrose ester of Group I (acetyl group on C3 of fructose and sucrose ester of Group II (no acetyl group on either glucose or fructose. Saturated fatty acid constituents were found to range from a maximum total of 18 carbons to a minimum total of 13 carbons. Unsaturated and isomeric fatty acid homologues were detected within the Group II sucrose ester.

This paper reports the development of the separation of vegetable oil triglycerides (TG) in supercritical chromatography (SFC), using superficially porous particles (SPPs). The SPP, having a small diameter (2-3μm), provide a higher theoretical plate number (N), which allows to improve separation of critical pairs of compounds. However, compared to fully porous particles of larger diameter (5μm), the pressure drop is also increased. Fortunately, supercriticalfluids have a low viscosity, which allows coupling several columns to achieve high N values, while maintaining flow rate above 1ml/min, ensuring a ultra high efficiency (UHE) at low pressure (LP) (below 40MPa), with regards to the one reached with liquid and sub-two micron particles (around 100MPa). The use of two detector systems (UV and ELSD) connected in series to the UHE-LP-SFC system provides complementary responses, due to their specific detection principles. Working in a first part with three coupled Kinetex C18 columns (45cm total length), the effect of modifier nature and percentage were studied with two reference oils, argan and rapeseed, chosen for their different and well-known TG composition. The analytical method was developed from previous studies performed with fully porous particles (FPP). Optimized conditions with three Kinetex were as follows: 17°C, 12% of ACN/MeOH (90/10; v/v). With these conditions, and by using an increased length of Kinetex C18 column (60cm), another additional column was selected from ten different commercial SPP C18 bonded phases, by applying a Derringer function on varied parameters: theoretical plate number (TPN), separation index (SI) for critical pairs of peaks (the peaks of compounds difficult to separate due to subtle structural differences), the analysis duration, and the total peak number. This function normalizes the values of any parameters, between 0 and 1, from the worst value to the better, allowing to take account of various parameters in the final

Full Text Available Olive leaves and tree bark were extracted through supercriticalfluid extraction (SFE and the chemical composition of the extracted mixture was determined by Gas Chromatography–Mass Spectrometry (GC–MS. Both samples contain a great number of triterpenes as squalene, which were used since 1997 as a main constituent of the flu vaccine (FLUAD, and the alpha-tocopherol the most biologically active form of vitamin E. We also underline the presence of many aliphatic compounds such nonacosane and heptacosane in low concentrations. The extractions were carried out at 313 and 333 K, at a pressure varying from 90 to 250 bars and using pure carbon dioxide in its supercritical phase. Therefore, their solubilities at equilibrium were numerically optimized via two assumptions and compared with the experimental values. Indeed, a good agreement between several results was shown.

Full Text Available The technique of supercriticalfluid extraction (SFE was applied to various sample matrices under a range of supercritical carbon dioxide (scCO2 densities and chamber temperatures. The purpose was to develop an effective extraction condition for the removal of eight target monoterpenes from Australian tea tree (Melaleuca alternifolia Cheel leaves. The optimum conditions for extraction were found to be 0.25 g/mL scCO2 density at a chamber temperature of 110oC. These condition were most effective when applied to whole fresh and rehydrated whole dried leaves, where it yielded maximum recovery of target analytes with minimum change in oil composition for the extractor system employed. This study demonstrates the importance of the type of sample matrix used in SFE work, and that a different extraction protocol would need to be developed for each matrix.

超临界流体中的化学反应可分为两大类，即超临界流体作为反应介质的反应和超临界流体作为反应原料的反应，分别介绍了其研究进展，着重介绍了第一类反应中的酶催化反应、超临界水氧化、高分子合成。%The progress of the reactions in supercriticalfluids, which were classified into two sorts, was reviewed. Biocatalysis in supercritical CO2, supercritical water oxidation and synthesis in supercriticalfluids were introduced in detail.

Various technologies pertaining to tuning composition of a fluid mixture in a supercritical Brayton cycle power generation system are described herein. Compounds, such as Alkanes, are selectively added or removed from an operating fluid of the supercritical Brayton cycle power generation system to cause the critical temperature of the fluid to move up or down, depending upon environmental conditions. As efficiency of the supercritical Brayton cycle power generation system is substantially optimized when heat is rejected near the critical temperature of the fluid, dynamically modifying the critical temperature of the fluid based upon sensed environmental conditions improves efficiency of such a system.

The IDDP is being carried out by an international industry-government consortium in Iceland (consisting of three leading Icelandic power companies, together with the National Energy Authority), Alcoa Inc. and StatoilHydro) with the objective of investigating the economic feasibility of producing electricity from supercritical geothermal fluids. This will require drilling to temperatures of 400-600°C and depths of 4 to 5 km. Modeling suggests that supercritical water could yield an order of magnitude greater power output than that produced by conventional geothermal wells. The consortium plans to test this concept in three different geothermal fields in Iceland. If successful, major improvements in the development of high-temperature geothermal resources could result worldwide. In June 2008 preparation of the first deep IDDP well commenced in the Krafla volcanic caldera in the active rift zone of NE Iceland. Selection of the first drill site for this well was based on geological, geophysical and geochemical data, and on the results of extensive geothermal drilling since 1971. During 1975-1984, a rifting episode occurred in the caldera, involving 9 volcanic eruptions. In parts of the geothermal field acid volcanic gases made steam from some of the existing wells unsuitable for power generation for the following decade. A large magma chamber at 3-7 km depth was detected by S-wave attenuation beneath the center of the caldera, believed to be the heat source of the geothermal system. A recent MT-survey has confirmed the existence of low resistivity bodies at shallow depths within the volcano. The IDDP well will be drilled and cased to 800m depth in September, before the winter snows, and in spring 2009 it will be drilled and cased to 3.5km depth and then deepened to 4.5 km in July. Several spot cores for scientific studies will be collected between 2400m and the total depth. After the well heats, it will be flow tested and, if successful, a pilot plant for power

The reactive behavior of a multiphase fluid (supercritical CO{sub 2} and brine) under physical-chemical conditions relevant to geologic storage and sequestration in a carbon repository is largely unknown. Experiments were conducted in a flexible cell hydrothermal apparatus to evaluate multiphase fluid-rock (aquifer plus caprock) reactions that may impact repository integrity.

Curcumin is the major constituent of turmeric (Curcuma longa L.). It has attracted widespread attention for its anticancer and anti-inflammatory activities. The separation of curcumin and its two close analogs, demethoxycurcumin and bisdemethoxycurcumin, has been challenging by conventional techniques. In this study, an environmentally friendly method based on supercriticalfluid chromatography was established for the rapid and facile separation of the three curcuminoids directly from the methanol extract of turmeric. The method was first developed and optimized by ultra performance convergence chromatography, and was then scaled up to preparative supercriticalfluid chromatography. Eluted with supercriticalfluid CO2 containing 8-15% methanol (containing 10 mM oxalic acid) at a flow rate of 80 mL/min, curcumin, demethoxycurcumin and bisdemethoxycurcumin could be well separated on a Viridis BEH OBD column (Waters, 250 mm × 19 mm, 5 μm) within 6.5 min. As a result, 20.8 mg of curcumin (97.9% purity), 7.0 mg of demethoxycurcumin (91.1%), and 4.6 mg of bisdemethoxycurcumin (94.8%) were obtained after a single step of supercriticalfluid chromatography separation with a mean recovery of 76.6%. Showing obvious advantages in low solvent consumption, large sample loading, and easy solvent removal, supercriticalfluid chromatography was proved to be a superior technique for the efficient separation of natural products.

Supercriticalfluid carbon dioxide (SF-CO{sub 2}) was chosen to study SupercriticalFluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO{sub 2}. A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO{sub 2} phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercriticalfluid extraction of uranium was studied in SF-CO{sub 2}. For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO{sub 2}. These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO{sub 2} for the extraction of uranium from ash. (author)

Preparative chromatography is a key technology for the separation of fine chemicals in production scale. Most of the published studies are carried out using liquid solvents as mobile phase. However, the used organic solvents can often be replaced by supercriticalfluids. A reduction or renouncement of organic solvents does not only correspond to the trend of the so-called green chemistry--a sustainable, environmentally friendly production of chemical products. But a changeover to chromatography with supercriticalfluids can also be reasonable under economic criteria. In this contribution a comparison between the Batch-supercriticalfluid chromatography (Batch-SFC) process and the simulated moving bed (SMB)-SFC process is presented. Because of the minor importance of solvent consumption and solvent recovery in SFC, the separation systems were optimized primarily in terms of their specific productivity. For three of the four investigated model systems, the specific productivity of the SMB process is significantly higher than the productivity of the Batch process. Due to the fact, that the process with the higher specific productivity is not inevitably the more economical process, supplementary the costs of the process were considered. Therefore the comparison of the two processes was done from an economic point of view considering the minimum product price that has to be realized to fulfill the defined economic aim. It was found that although the optimized specific productivities of the SMB process were significantly higher than the productivities of the Batch process, the Batch process is the more profitable process for the investigated production rate range between 0.4 and 5t/a.

Waste hops are good sources offlavonoids. Extraction offlavonoids from waste hops (SC-CO2 extracted hops) using supercriticalfluids technology was investigated. Various temperatures, pressures and concentrations of ethanol (modifier) and the ratio (w/w) of solvent to material were tested in this study. The results of single factor and orthogonal experiments showed that at 50℃, 25 MPa, the ratio of solvent to material (50%), ethanol concentration (80%) resulted in maximum extraction yield flavonoids (7.8 mg/g). HPLC-MS analysis of the extracts indicated that flavonoids obtained were xanthohumol, the principal prenylflavonoid in hops.

The enantiomers of methamphetamine were differentiated by supercriticalfluid chromatography (SFC) with an enantioselective cellulose-based packed column. The optimization of the chromatographic conditions was achieved by changing column temperature, co-solvent proportion, additive concentration, flow rate and back pressure. In particular, the additive concentration crucially changed the resolution between the enantiomers. After determining the optimized conditions, the enantiomers of methamphetamine were successfully separated. The analytical precision, accuracy and limit of detection were checked by using the authentic standard and seized real samples. We believe that chiral SFC is a promising method for enantioseparation of forensic samples.

In the present paper is reported the method for the isolation and extraction of total flavonoids of Epimedium Koreanum Nakai by means of supercriticalfluid extraction(SFE). By examining pressure, temperature, amounts of modifier and extraction time, the optimized condition of SFE is confirmed as 30 MPa and 60 ℃, with 70% ethanol as the modifier. The samples were statically extracted for 30 min, followed by dynamic extraction for 120 min at a flow rate of 6 mL/min. The quantitative analysis of total flavonoids was performed by UV-Vis spectrophotometry. Compared with the conventional method, the SFE method is more efficient, more rapid and more friendly environmentally.

A new microcellular composite material with a biomimetic structure has been prepared via the supercriticalfluid (SCF) technology. The resultant material has a clear biomimetic structure like bamboo and wood. The skin region is enriched with oriented high-strength thermotropic liquid crystal polymer fibrils, while the core region with polystyrene (PS) micro-cells. The diameter and density of micro- cells can be controlled by the processing parameters such as temperature and pressure. And the skin thickness can be controlled conveniently by varying the composition of polystyrene and liquid crystal polymer.

Capillary supercriticalfluid chromatographic (SFC) method has been developed for the determination of panaxadiol and panaxatriol in ginseng and its preparations. 0.1 g ginseng or an appropriate amount of its preparations was hydrolysed by 15% H2SO4 in an ethanol:water (1:1 v/v) solution for 4 h followed by 15% NaOH for 0.5 h. The mixture was extracted by cyclohexane. The cyclohexane extracts were purified by a partition column and concentrated by an adsorption column and then analysed by SFC. Methyltestosterone was used as the internal standard.

To study the extraction technology of epigoitri from Isatidis Radix by supercritical CO2 fluid. The effects of pressure, temperature, time, concentration and dosage of alcohol were studied by single factor analysis and orthogonal test. The optimized conditions were as follows: The pressure was 20 MPs, the temperature was 50 degrees C, the time was 2 h, concentration of alcohol was 100%, dosage was 80 mL. The content of epigoitri in the extract could reach 38.63% under the above conditions. This method is simple, rapid and it is suitable for the extraction of epigoitri from Isatidis Radix.

Supercriticalfluid chromatography (SFC) is increasingly being recognized as a powerful technique for analysis of pharmaceutical compounds in various dosage forms. Assay of aqueous formulations of research compounds by SFC is, however, a relatively unexplored area primarily due to the potential problems associated with it. This work describes the development of a direct assay of a chiral drug compound AZY in a 100% aqueous formulation by SFC, and its qualification following ICH and FDA validation guidelines on chromatographic methods. The results indicated that SFC has the potential for assaying aqueous formulations of research compounds with high degree of selectivity, accuracy, precision, robustness, sensitivity, and linearity over a wide range of concentrations. This work also confirmed a previous hypothesis that direct formulation assay by SFC approach is applicable to both acidic and basic pharmaceutical compounds with equal degree of success.

Separation of enantiomers by means of high-performance liquid chromatography (HPLC), supercriticalfluid chromatography (SFC), and capillary electrochromatography (CEC) is of great importance in pharmaceutical analyses. In recent years, separation of various types of racemates employs most frequently chiral stationary phases based on macrocyclic antibiotics. This class of chiral selectors includes vancomycin, teikoplanin, ristocetin A, teikoplanin without saccharide components, avoparcin, etc. The review paper describes the properties of selected antibiotics, the effect of chromatographic conditions on enantioselectivity (effect of the composition of the mobile phase, effect of pH of the mobile phase, effect of temperature), and the study of possible mechanisms of interaction, which play an important role in the separation of enantiomers. Examples of the use of macrocyclic antibiotics in the separation of various compounds by means of the HPLC, SFC, and CEC methods follow.

Poor aqueous solubility of drug candidates is a major challenge for the pharmaceutical scientists involved in drug development. Particle size reduction appears as an effective and versatile option for solubility improvement. Nanonization is an attractive solution to improve the bioavailability of the poorly soluble drugs, improved therapies, in vivo imaging, in vitro diagnostics and for the production of biomaterials and active implants. In drug delivery, application of nanotechnology is commonly referred to as Nano Drug Delivery Systems (NDDS). In this article, commercially available nanosized drugs, their dosage forms and proprietors, as well as the methods used for preparation like milling, high pressure homogenization, vacuum deposition, and high temperature evaporation were listed. Unlike the traditional methods used for the particle size reduction, supercriticalfluid-processing techniques offer advantages ranging from superior particle size control to clean processing. The primary focus of this review article is the use of supercritical CO2 based technologies for small particle generation. Particles that have the smooth surfaces, small particle size and distribution and free flowing can be obtained with particular SCF techniques. In almost all techniques, the dominating process variables may be thermodynamic and aerodynamic in nature, and the design of the particle collection environment. Rapid Expansion of Supercritical Solutions (RESS), Supercritical Anti Solvent (SAS) and Particles from Gas Saturated Solutions (PGSS) are three groups of processes which lead to the production of fine and monodisperse powders. Few of them may also control crystal polymorphism. Among the aforementioned processes, RESS involves dissolving a drug in a supercriticalfluid (SCF) and passing it through an appropriate nozzle. Rapid depressurization of this solution causes an extremely rapid nucleation of the product. This process has been known for a long time but its application

This report describes the first results of SupercriticalFluid Extraction (SFE) as technique for the extraction of organic components from soil. SFE is based on the extraction properties of supercriticalfluids - in this case CO2 - having liquidlike as well as gaslike behaviour as their low

The characteristic of solid radioactive wastes containing less 1% uranium, such as mine tailings, contaminated soil and sludge, is complex matrix and irregular surface. The traditional treatment technology usually consumes a lot of chemical reagents and produces a large amount of secondary wastes. The supercriticalfluid has the advantage of high diffusivity, low viscosity, and liquid-like solvating capability, which enable the supercritical carbon dioxide fluid extraction (SFE) technology to be a alternative method to extract micro amount of uranium from solid radioactive wastes.

A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

In the synthesis of metal oxide fine particles by continuous supercritical hydrothermal method, the particle characteristics are greatly affected by not only the reaction conditions (temperature, pressure, residence time, concentration, etc.), but also the heating rate from ambient to reaction temperature. Therefore, the heating method by direct mixing of starting solution at room temperature with supercritical water is a key technology for the particle production having smaller size and narrow distribution. In this paper, mixing engineering study through comparison between conventional T-shaped mixers and recently developed swirl mixers was carried out in the hydrothermal synthesis of NiO nanoparticles from Ni(NO3)2 aqueous solution at 400 °C and 30 MPa. Inner diameter in the mixers and total flow rates were varied. Furthermore, the heating rate was calculated by computational fluid dynamics (CFD) simulation. Relationship between the heating rate and the average particle size were discussed. It was clarified that the miniaturization of mixer inner diameter and the use of the swirl flow were effective for improving mixing performance and contributed to produce small and narrow distribution particle under same experimental condition of flow rate, temperature, pressure, residence time, and concentration of the starting materials. We have focused the mixer optimization due to a difference in fluid viscosity.

Using xylene as supercriticalfluids (SCFs) media and polydimethylsilane (PDMS) as raw material, the ceramic precursor polycarbosilane (PCS) with moderate mo-lecular weight and narrow molecular weights distribution was synthesized under high pressure and temperature in autoclave. Softening-point test, Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), element analysis and the yield test of PCS were adopted to characterize the SCFs-method and compared with two other PCS synthesis methods named normal-pressure high-temperature (NP) method and high-pressure hith-temperature (HP) method. The results indicate that the PCS maintains a high Si-H content and its chemical formula is SiC1.91H7.27O0.05. The yield is 63.5 wt% which has been improved by about 20 wt%, the softening-point is 180―220 ℃, the number average molecular weight is 1477 and the molecular weights distribution index is 1.61. The synthesis method via supercriticalfluids with good diathermancy and reaction uniformity is a new feasi-ble method of synthesizing PCS with good qualities.

Analysis and production of enantiomerically pure compounds is a major topic of interest when active pharmaceutical ingredients are concerned. Enantioselective chromatography has become a favourite both at the analytical and preparative scales. High-performance liquid chromatography (HPLC) and supercriticalfluid chromatography (SFC) are dominating the scene and are often seen as complementary techniques. Nowadays, for economic and ecologic reasons, SFC may be preferred over normal-phase HPLC (NPLC) as it allows significant reductions in solvent consumption. However, the transfer of NPLC methods to SFC is not always straightforward. In this study, we compare the retention of achiral molecules and separation of enantiomers under supercriticalfluid (carbon dioxide with ethanol or isopropanol) and liquid normal-phase (heptane with ethanol or isopropanol) elution modes with polysaccharide stationary phases in order to explore the differences between the retention and enantioseparation properties between the two modes. Chemometric methods (namely quantitative structure-retention relationships and discriminant analysis) are employed to compare the results obtained on a large set of analytes (171 achiral probes and 97 racemates) and gain some understanding on the retention and separation mechanisms. The results indicate that, contrary to popular belief, carbon dioxide - solvent SFC mobile phases are often weaker eluents than liquid mobile phases. It appears that SFC and NPLC elution modes provide different retention mechanisms. While some enantioseparations are unaffected, facilitating the transfer between the two elution modes, other enantioseparations may be drastically different due to different types and strength of interactions contributing to enantioselectivity.

The coating properties of a novel water stationary phase used in capillary supercriticalfluid chromatography were investigated. The findings confirm that increasing the length or internal diameter of the type 316 stainless-steel column used provides a linear increase in the volume of stationary phase present. Under normal operating conditions, results indicate that about 4.9 ± 0.5 μL/m of water phase is deposited uniformly inside of a typical 250 μm internal diameter 316 stainless-steel column, which translates to an area coverage of about 6.3 ± 0.5 nL/mm(2) regardless of dimension. Efforts to increase the stationary phase volume present showed that etching the stainless-steel capillary wall using hydrofluoric acid was very effective for this. For instance, after five etching cycles, this volume doubled inside of both the type 304 and the type 316 stainless-steel columns examined. This in turn doubled analyte retention, while maintaining good peak shape and column efficiency. Overall, 316 stainless-steel columns were more resistant to etching than 304 stainless-steel columns. Results indicate that this approach could be useful to employ as a means of controlling the volume of water stationary phase that can be established inside of the stainless-steel columns used with this supercriticalfluid chromatography technique.

Using xylene as supercriticalfluids (SCFs) media and polydimethylsilane (PDMS) as raw material, the ceramic precursor polycarbosilane (PCS) with moderate mo- lecular weight and narrow molecular weights distribution was synthesized under high pressure and temperature in autoclave. Softening-point test, Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), element analysis and the yield test of PCS were adopted to characterize the SCFs-method and compared with two other PCS synthesis methods named normal-pressure high-temperature (NP) method and high-pressure hith-temperature (HP) method. The results indicate that the PCS maintains a high Si-H content and its chemical formula is SiC1.91H7.27O0.05. The yield is 63.5 wt% which has been improved by about 20 wt%, the softening-point is 180-220℃, the number average molecular weight is 1477 and the molecular weights distribution index is 1.61. The synthesis method via supercriticalfluids with good diathermancy and reaction uniformity is a new feasi- ble method of synthesizing PCS with good qualities.

The proline derived diketopiperazine has been identified in plants, insects and fungi with unknown function and was recently also reported as the first pheromone from a diatom. Nevertheless the stereochemistry and enantiomeric excess of this natural product remained inaccessible using direct analytical methods. Here we introduce a chiral separation of this metabolite using supercriticalfluid chromatography/mass spectrometry. Several chromatographic methods for chiral analysis of the diketopiperazine from the diatom Seminavis robusta and synthetic enantiomers have been evaluated but neither gas chromatography nor high performance liquid chromatography on different chiral cyclodextrin phases were successful in separating the enantiomers. In contrast, supercriticalfluid chromatography achieved baseline separation within four minutes of run time using amylose tris(3,5-dimethylphenylcarbamate) as stationary phase and 2-propanol/CO2 as mobile phase. This very rapid chromatographic method in combination with ESI mass spectrometry allowed the direct analysis of the cyclic dipeptide out of the complex sea water matrix after SPE enrichment. The method could be used to determine the enantiomeric excess of freshly released pheromone and to follow the rapid degradation observed in diatom cultures. Initially only trace amounts of c(d-Pro-d-Pro) were found besides the dominant c(l-Pro-l-Pro) in the medium. However the enantiomeric excess decreased upon pheromone degradation within few hours indicating that a preferential conversion and thus inactivation of the l-proline derived natural product takes place.

Based on the solubility in supercritical CO2, two strategies in which CO2 plays different roles are used to make quercetine and astaxanthin particles by supercriticalfluid technologies. The experimental results showed that micronized quercetine particles with mean particle size of 1.0-1.5 um can be made via solution enhanced dis-persion by supercriticalfluids (SEDS) process, in which CO2 worked as turbulent anti-solvent; while for astaxan-thin, micronized particles with mean particle size of 0.3-0.8 um were also made successfully by rapid expansion supercritical solution (RESS) process.

Mesoporous zirconia was synthesized by a new and simple method.Zirconium n-propoxide was used as the zirconium source.A small,inexpensive nonsurfactant,triethanolamine,was used as the template.The template was removed by thermal treatment in air and supercriticalfluid extraction using CO2.The structure of the resulting materials was characterized by X-ray diffraction,transmission electron microscopy,and N2 adsorption-desorption analyses.The materials are found to have narrowly distributed average pore diameters and wormhole-like pore channels.However,higher surface area and larger pore volume are exhibited after supercdtical fluid extraction with CO2.The removal of the template by thermal treatment also leads to condensation and mild shrinkage of the zirconia framework.

Essential oils and fatty acids of Descurainia sophia L. seed were obtained by supercritical CO2 extraction and steam distillation methods. The effect of different parameters such as pressure, temperature, modifier volume, dynamic and static extraction timeon the extraction yield were optimized using a central composite design after a 2 (n-1) fractional factorial design. The results showed that under the pressure of 355 bar, temperature of 65 °C, methanol volume of 150 μL, dynamic and static extraction times of 35 and 10 min, respectively, the major components were methyl linoleate (18.2 %), camphor (12.32 %), cis-thujone (11.3 %) and trans-caryophyllene (9.17 %). The results indicated that by using the proper conditions, the supercriticalfluid extraction is more selective than the steam distillation method. Extraction yields based on supercriticalfluid extraction varied in the range of 0.68 to 17.1 % (w/w), and the extraction yield based on the steam distillation was 0.25 % (v/w).

In recent years, SupercriticalFluid Extraction (SFE) technique has been widely used for the extraction of metal ions. In the present study, extraction of uranium from nitric acid medium was investigated using supercritical carbon dioxide (Sc-CO{sub 2}) containing various organophosphorous compounds such as trialkyl phosphates e.g. tri-iso-amyl phosphate (TiAP), tri-sec-butyl phosphate (TsBP) and tri-n-butyl phosphate (TBP), dialkylalkyl phosphonates, e.g. diamylamyl phosphonate (DAAP) and dibutyl butyl phosphonate (DBBP), dialkyl hydrogen phosphonates, e.g. dioctyl hydrogen phosphonate (DOHP), dioctylphosphineoxide (DOPO), trioctyl phosphine oxide (TOPO), n-octylphenyl N,N-diisobutyl carbamoylmethylphosphine oxide (CMPO) and di-2-ethyl-hexyl phosphoric acid (HDEHP). Some of these ligands have been investigated for the first time in the supercritical phase for the extraction of uranium. The extraction efficiency of uranium was studied with TiAP, DAAP and DBBP as a function of nitric acid concentration; the kinetics of the equilibration period (static extraction) and transportation of the metal complex (dynamic extraction) was investigated. The influence of pressure and temperature on the extraction behaviour of uranium with DAAP was studied from 4 N HNO{sub 3}. The extraction efficiency of uranium from 4 N nitric acid medium was found to increase in the order of phosphates < phosphonates < HDEHP < TOPO < CMPO. In the case of phosphates and phosphonates, the maximum extraction of uranium was found to be from 4 N HNO{sub 3} medium. The acidic extractants, HDEHP and DOHP showed relatively higher extraction at lower acidities. The relative extraction of uranium and thorium from their mixture was also examined using Sc-CO{sub 2} containing phosphates, phosphonates and TOPO. The ligand, TsBP provided better fractionation between uranium and thorium compared to trialkyl phosphates, dialkyl alkyl phosphonates and TOPO.

An artificial Radial Basis Function (RBF) neural network model was developed for the prediction of mass transfer of the phospholipids from canola meal in supercritical CO2 fluid. The RBF kind of artificial neural networks (ANN) with orthogonal least squares (OLS) learning algorithm were used for mod...

Medicinal chemists often depend on analytical instrumentation for reaction monitoring and product confirmation at all stages of pharmaceutical discovery and development. To obtain pure compounds for biological assays, the removal of side products and final compounds through purification is often necessary. Prior to purification, chemists often utilize open-access analytical LC/MS instruments because mass confirmation is fast and reliable, and the chromatographic separation of most sample constituents is sufficient. Supercriticalfluid chromatography (SFC) is often used as an orthogonal technique to HPLC or when isolation of the free base of a compound is desired. In laboratories where SFC is the predominant technique for analysis and purification of compounds, a reasonable approach for quickly determining suitable purification conditions is to screen the sample against different columns. This can be a bottleneck to the purification process. To commission SFC for open-access use, a walk-up analytical SFC/MS screening system was implemented in the medicinal chemistry laboratory. Each sample is automatically screened through six column/method conditions, and on-demand data processing occurs for the chromatographers after each screening method is complete. This paper highlights the "FastTrack" approach to expediting samples through purification.

Numerical solutions of the Euler equations using real gas equations of state (EOS) often exhibit serious inaccuracies. The focus here is the van der Waals EOS and its variants (often used in supercriticalfluid computations). The problems are not related to a lack of convexity of the EOS since the EOS are considered in their domain of convexity at any mesh point and at any time. The difficulties appear as soon as a density discontinuity is present with the rest of the fluid in mechanical equilibrium and typically result in spurious pressure and velocity oscillations. This is reminiscent of well-known pressure oscillations occurring with ideal gas mixtures when a mass fraction discontinuity is present, which can be interpreted as a discontinuity in the EOS parameters. We are concerned with pressure oscillations that appear just for a single fluid each time a density discontinuity is present. The combination of density in a nonlinear fashion in the EOS with diffusion by the numerical method results in violation of mechanical equilibrium conditions which are not easy to eliminate, even under grid refinement. A cure to this problem is developed in the present paper for the van der Waals EOS based on previous ideas. A special extra field and its corresponding evolution equation is added to the flow model. This new field separates the evolution of the nonlinear part of the density in the EOS and produce oscillation free solutions. The extra equation being nonconservative the behavior of two established numerical schemes on shocks computation is studied and compared to exact reference solutions that are available in the present context. The analysis shows that shock conditions of the nonconservative equation have important consequence on the results. Last, multidimensional computations of a supercritical gas jet is performed to illustrate the benefits of the present method, compared to conventional flow solvers.

Analyses of complex samples of cosmetics, such as creams or lotions, are generally achieved by HPLC. These analyses are often multistep gradients, due to the presence of compounds with a large range of polarity. For instance, the bioactive compounds may be polar, while the matrix contains lipid components that are rather non-polar, thus cosmetic formulations are usually oil-water emulsions. Supercriticalfluid chromatography (SFC) uses mobile phases composed of carbon dioxide and organic co-solvents, allowing for good solubility of both the active compounds and the matrix excipients. Moreover, the classical and well-known properties of these mobile phases yield fast analyses and ensure rapid method development. However, due to the large number of stationary phases available for SFC and to the varied additional parameters acting both on retention and separation factors (co-solvent nature and percentage, temperature, backpressure, flow rate, column dimensions and particle size), a simplified approach can be followed to ensure a fast method development. First, suited stationary phases should be carefully selected for an initial screening, and then the other operating parameters can be limited to the co-solvent nature and percentage, maintaining the oven temperature and back-pressure constant. To describe simple method development guidelines in SFC, three sample applications are discussed in this paper: UV-filters (sunscreens) in sunscreen cream, glyceryl caprylate in eye liner and caffeine in eye serum. Firstly, five stationary phases (ACQUITY UPC(2)) are screened with isocratic elution conditions (10% methanol in carbon dioxide). Complementary of the stationary phases is assessed based on our spider diagram classification which compares a large number of stationary phases based on five molecular interactions. Secondly, the one or two best stationary phases are retained for further optimization of mobile phase composition, with isocratic elution conditions or, when

The deposition of a Cu seed layer film is investigated by supercriticalfluid deposition (SCFD) using H2 as a reducing agent for Bis(2,2,6,6-tetramethyl-3,5-heptanedionato) copper in supercritical CO2 (scCO2).The effects of deposition temperature,precursor,and H2 concentration are investigated to optimize Cu deposition.Continuous metallic Cu films are deposited on Ru substrates at 190 ℃ when a 0.002 mol/L Cu precursor is introduced with 0.75 mol/L H2.A Cu precursor concentration higher than 0.002 mol/L is found to have negative effects on the surface qualities of Cu films.For a H2concentration above 0.56 mol/L,the root-mean-square (RMS) roughness of a Cu film decreases as the H2 concentration increases.Finally,a 20-nm thick Cu film with a smooth surface,which is required as a seed layer in advanced interconnects,is successfully deposited at a high H2 concentration (0.75 mol/L).

Full Text Available Schisandra chinensis is a traditional Chinese medicine that has been used for treating insomnia and neurasthenia for centuries. Lignans, which are considered to be the bioactive components, are apt to be extracted by supercritical carbon dioxide. This study was conducted to investigate the sedative and hypnotic activities of the supercritical carbon dioxide fluid extraction of S. chinensis (SFES in mice and the possible mechanisms. SFES exhibited an obvious sedative effect on shortening the locomotor activity in mice in a dose-dependent (10–200 mg/kg manner. SFES (50 mg/kg, 100 mg/kg, and 200 mg/kg, intragstrically showed a strong hypnotic effect in synergy with pentobarbital in mouse sleep, and reversal of insomnia induced by caffeine, p-chlorophenylalanine and flumazenil by decreasing sleep latency, sleep recovery, and increasing sleeping time. In addition, it produced a synergistic effect with 5-hydroxytryptophan (2.5 mg/kg, intraperitoneally. The behavioral pharmacological results suggest that SFES has significant sedative and hypnotic activities, and the mechanisms might be relevant to the serotonergic and γ-aminobutyric acid (GABAergic system.

Valorisation of lignin plays a key role in further development of lignocellulosic biorefinery processes the production of biofuels and bio-based materials. In the present study, organosolv hardwood and wheat straw lignins were converted in a supercriticalfluid consisting of carbon dioxide/acetone/water (300-370°C, 100bar) to a phenolic oil consisting of oligomeric fragments and monomeric aromatic compounds with a total yield of 10-12% based on lignin. These yields are similar to the state-of-the-art technologies such as base-catalysed thermal processes applied for lignin depolymerisation. Addition of formic acid increases the yield of monomeric aromatic species by stabilizing aromatic radicals. Supercritical depolymerisation of wheat straw and hardwood lignin yielded monomeric compounds in different compositions with a maximum yield of 2.0% for syringic acid and 3.6% for syringol, respectively. The results of the present study showed that under the applied conditions competition occurred between lignin depolymerisation and recondensation of fragments.

Full Text Available Schinus molle L., also known as pepper tree, has been reported to have antimicrobial, antifungal, anti-inflammatory, antispasmodic, antipyretic, antitumoural and cicatrizing properties. This work studies supercriticalfluid extraction (SFE to obtain volatile and non-volatile compounds from the aerial parts of Schinus molle L. and the influence of the process on the composition of the extracts. Experiments were performed in a pilot-scale extractor with a capacity of 1 L at pressures of 9, 10, 12, 15 and 20 MPa at 323.15 K. The volatile compounds were obtained by CO2 supercritical extraction with moderate pressure (9 MPa, whereas the non-volatile compounds were extracted at higher pressure (12 to 20 MPa. The analysis of the essential oil was carried out by GC-MS and the main compounds identified were sabinene, limonene, D-germacrene, bicyclogermacrene, and spathulenol. For the non-volatile extracts, the total phenolic content was determined by the Folin-Ciocalteau method. Moreover, one of the goals of this study was to compare the experimental data with the simulated yields predicted by a mathematical model based on mass transfer. The model used requires three adjustable parameters to predict the experimental extraction yield curves.

the Euler, Froude, Reynolds, Weber, and Cauchy numbers are defined as essential tools for interpreting and using experimental data. The derivations of the energy and momentum equations are treated in detail. One-dimensional equations for steady nonuniform flow are developed, and the restrictions applicable to the equations are emphasized. Conditions of uniform and gradually varied flow are discussed, and the origin of the Chezy equation is examined in relation to both the energy and the momentum equations. The inadequacy of all uniform-flow equations as a means of describing gradually varied flow is explained. Thus, one of the definitive problems of river hydraulics is analyzed in the light of present knowledge. This report is the outgrowth of a series of short schools conducted during the spring and summer of 1953 for engineers of the Surface Water Branch, Water Resources Division, U. S. Geological Survey. The topics considered are essentially the same as the topics selected for inclusion in the schools. However, in order that they might serve better as a guide and outline for informal study, the arrangement of the writer's original lecture notes has been considerably altered. The purpose of the report, like the purpose of the schools which inspired it, is to build a simple but strong framework of the fundamentals of fluid mechanics. It is believed that this framework is capable of supporting a detailed analysis of most of the practical problems met by the engineers of the Geological Survey. It is hoped that the least accomplishment of this work will be to inspire the reader with the confidence and desire to read more of the recent and current technical literature of modern fluid mechanics.

Knowing the chemical compositions of fluid and melt is fundamental in understanding the magma genesis and chemical differentiation in the Earth's interior. We investigated the stability fields of aqueous fluid, silicate melt, and supercriticalfluid magma using in-situ x-ray radiography and the second critical endpoint in the system peridotite-H2O was determined to be around 3.8 GPa (Mibe et al., 2007, JGR). Using the quenched recovered samples obtained by Mibe et al. (2007), we determined the chemical compositions of aqueous fluid, silicate melt, and supercriticalfluid in the vicinity of the second critical endpoint in the system peridotite-H2O by EPMA analyses. A 10- to 30-μm diameter electron beam was used to obtain the composition of quenched materials from aqueous fluid, silicate melt, and supercriticalfluid. The compositions of coexisting aqueous fluid and silicate melt were determined at 3.3 GPa and 3.6 GPa and 1180°C. In both samples, olivine coexists with aqueous fluid and silicate melt. In the run at 3.3 GPa, the composition of aqueous fluid was high-Mg dacitic, whereas the composition of silicate melt was hydrous peridotite. In the run at 3.6 GPa, the composition of aqueous fluid was high-Mg andesitic, whereas the composition of silicate melt was hydrous komatiitic. Although aqueous fluids in both runs are high-Mg, both MgO and FeO preferentially enters into silicate melt compared to aqueous fluid.

Bac technology of extraction and kground of supercriticalfluid extraction technology was introduced and overview of the supercriticalfluid extraction was also introduced. Focused on the method of enhanced industrial applications of supercriticalfluid extraction technology.%简要介绍了超临界萃取技术的背景，并对超临界萃取技术做相关概述。着重介绍了强化萃取的方法和超临界萃取技术的工业应用。

We have studied the chromatographic behavior of the homologous series of alkylbenzenes (ranging from octylbenzene to octadecylbenzene) on the same C18 reversed-phase column in supercriticalfluid chromatography (SFC) and reversed phase liquid chromatography (RPLC) at various experimental conditions, such as different eluent compositions, flow-rates, and mobile phase densities. The first and the second moments of the peaks were used to estimate the overall mass-transfer processes in both chromatographic modes using the stochastic model of chromatography. The results confirm that in SFC - as the density of the mobile phase is influenced by the flow-rate - there is a broader variation of mass-transfer properties than in liquid chromatography. As expected, the optimum mobile phase velocity is higher in SFC, but there is no real difference in the minimum value of plate height, i.e. in the optimum efficiency.

Full Text Available The supercriticalfluid extraction of aroma compounds from basil (Ocimum basilicum L. was studied. Response surface methodology was used to optimize the parameters of the process. Full factorial design was applied to evaluate the effects of two independent variables (pressure and temperature on the extraction yield and linalool yield. From the response surface plots, pressure and temperature exhibited independent and interactive effect on the extraction yield. The optimal conditions to obtain the highest extraction yield (1.91% of O. basilicum were the pressure of 29.7 MPa and temperature of 59.2oC, whereas the highest yield of linalool (1.998 g•kg-1 was obtained at the pressure of 20 MPa and temperature of 40oC. The experimental values agreed with the predicted ones, indicating suitability of the response surface methodology for optimizing the extraction process. [Projekat Ministarstva nauke Republike Srbije, br. TR 31013

We study experimentally the flow stability of entangled polymer solutions extruded through glass capillaries. We show that the pipe flow becomes linearly unstable beyond a critical value (Wic≃5 ) of the Weissenberg number, via a supercritical bifurcation which results in a helical distortion of the extrudate. We find that the amplitude of the undulation vanishes as the aspect ratio L /R of the capillary tends to zero, and saturates for large L /R , indicating that the instability affects the whole pipe flow, rather than the contraction or exit regions. These results, when compared to previous theoretical and experimental works, lead us to argue that the nature of the instability is controlled by the level of shear thinning of the fluids. In addition, we provide strong hints that the nonlinear development of the instabiilty is mitigated, in our system, by the gradual emergence of gross wall slip.

Full Text Available Lycopene, an acyclic, open chain, unsaturated carotenoid having 13 double bonds, of which 11 are conjugated, arranged in a linear array, is considered to be a pigment of potential commercial importance in the emerging market for nutraceutical products because of its function as a health-promoting ingredient. Lycopene has received a great deal of attention as an effective antioxidant that can play an important role in reducing the risk of several chronic diseases. In this study, we reviewed extraction parameters of lycopene from tomato and tomato products by supercriticalfluids and pre-extraction procedures. For extraction, temperature range as 50-110°C, extraction time range as 0.5-8.0 hours, extraction pressure range as 300-400 bar and using co-solvent, especially ethanol, are common parameters.

In this study, supercriticalfluid extraction has been successfully applied to a sequential fractionation of fatty acids and polyphenols from wine wastes (2 different vitis vinifera grapes). To this aim, in a 1st step just fatty acids were extracted and in a 2nd one the polyphenols. The variables that affected to the extraction efficiency were separately optimized in both steps following an experimental design approach. The effect of extraction temperature flow, pressure, and time were thoroughly evaluated for the extraction of fatty acids, whereas the addition of methanol was also considered in the case of the polyphenols extraction. A quantitative extraction with high efficiency was achieved at a very short time and low temperatures. Concerning quantification, fatty acids were determined by means of gas chromatography coupled to mass spectrometry after a derivatization step, whereas the polyphenols were analyzed by means of high performance liquid chromatography coupled to tandem mass spectrometry and the Folin-Ciocalteu method.

Supercriticalfluid chromatography (SFC) has long been a preferred method for enantiopurity analysis in support of pharmaceutical discovery and development, but implementation of the technique in regulated GMP laboratories has been somewhat slow, owing to limitations in instrument sensitivity, reproducibility, accuracy and robustness. In recent years, commercialization of next generation analytical SFC instrumentation has addressed previous shortcomings, making the technique better suited for GMP analysis. In this study we investigate the use of modern SFC for enantiopurity analysis of several pharmaceutical intermediates and compare the results with the conventional HPLC approaches historically used for analysis in a GMP setting. The findings clearly illustrate that modern SFC now exhibits improved precision, reproducibility, accuracy and robustness; also providing superior resolution and peak capacity compared to HPLC. Based on these findings, the use of modern chiral SFC is recommended for GMP studies of stereochemistry in pharmaceutical development and manufacturing.

To extract praeruptorin A from Radix Peucedani by supercriticalfluid extraction (SFE)-CO2. After preliminary experiment, three main factors were acquired that could influence the result of SFE-CO2, including the time, pressure and temperature of the extraction. The optimal extraction process was carried out on orthogonal design, and SFE-CO2 was compared with the traditional methods. In the extraction of the praeruptorin A, the best extraction conditions were 60 degrees C, 20 MPa, and duration for three hours. As cosolvent alcohol was added, the amount of extraction of the praeruptorin A increased, and the amount of SFE-CO2 extraction was higher than those of decoction and heating reflux. The SFE-CO2 in extracting praeruptorin A from Radix Peucedani is feasible and reliable.

This article focuses on the state-of-the-art in sample preparation using supercriticalfluid extraction (SFE), to monitor the content of polyhalogenated pollutants in aquaculture and marine environmental samples. Marine sediments and biological applications, including several types of samples matrices (fish, shellfish, seaweed and fish feed) and analyte groups (polychlorinated biphenyls (PCBs), polybrominated biphenyls (PBBs), polybrominated diphenylethers (PBDEs), polychlorinated dibenzo-p-dioxin (PCDD)/Fs and organochlorinated pesticide (OCPs)) are discussed with respect to SFE use and optimisation of conditions. We also discuss the great analytical potential of SFE, the integration of the extraction and clean-up steps for rapid sample processing justifying its use for routine work. The most recent SFE applications to the determination of these pollutants in marine environmental (biota and sediment) samples, published in the last 15 years, are reviewed.

The efficiencies of extraction of vapor-deposited pyrene from a high-carbon coal stack ash by Soxhlet extraction with methanol, ultrasonic extraction with toluene, acid pretreatment and subsequent ultrasonic extraction with toluene, batch extraction with toluene, and supercriticalfluid extraction (SFE) are compared. SFE using CO(2) or isobutane yielded extraction recoveries virtually identical with those obtained using ultrasonic or Soxhlet extraction processes. Collection of the SFE extract was performed by expansion into a solvent or onto the head of a gas chromatography (GC) column. No loss of extracted pyrene was observed upon collection of methanol-modified CO(2) SFE by expansion into methanol. Also, no loss of pure CO(2) SFE extract was observed upon collection on the head of a GC column. However, use of a methanol or toluene modifier for CO(2) SFE directly coupled to GC effected complete loss of extracted pyrene.

A common complication in fabricating arrays of TiO(2) nanotubes is that they agglomerate into tightly packed bundles during the inevitable solvent evaporation step. This problem is particularly acute for template-fabricated TiO(2) nanotubes, as the geometric tunability of this technique enables relatively large inter-pore spacings or, from another perspective, more space for lateral displacement. Our work showed that agglomeration results from the surface tension forces that are present as the ambient solvent is evaporated from the nanotube film. Herein, we report a processing and fabrication approach that utilizes supercriticalfluid drying (CO(2)) to prepare arrays of template-fabricated TiO(2) nanotubes that are free-standing and spatially isolated. This approach could be beneficial to many emerging technologies, such as solid-state dye-sensitized solar cells and vertically-oriented carbon nanotube electrodes.

Full Text Available Subcritical and supercritical extractions are novel, non destructive techniques which can be applied for the removal of hazardous compounds from contaminated soil without any changes of the soil composition and structure. The aim of the presented review paper is to give information on up-to day results of this method commonly applied by several institutions worldwide. Interest in the application of SC CO2 has been more expressed in the last two decades, which may be related to its favorable characteristics (non-toxic, non-flammable, increase diffusion into small pores, low viscosity under SC conditions, low price and others. However, interest in wet oxidation (WO and especially in SCWO (the application of water under supercritical conditions with air has also increased in the last few years. Interest in H2O as a SC fluid, as well as in extraction with water under subcritical conditions may also be related to specific characteristics and the enhanced rate of extraction. Moreover, the solubility of some specific compounds present in soil can be easily changed by adjusting the pressure and temperature of extraction. The high price of the units designed to operate safely at a pressure and temperature much higher than the a critical one of the applied fluids is the main reason why, at present, there is no more broader application of such techniques for the removal hazardous materials from contaminated soil. In the present paper, among many literature citations and their overall review, some specific details related to the development of specific analytical methods under SC conditions are also considered.

Highlights: •Nanoparticles of Pd were deposed on the binary compound Mg{sub 0.65}Sc{sub 0.35} using the SupercriticalFluid Chemical Deposition (SFCD) method. •Numerous parameters were tested and optimized in order to obtain a homogeneous deposition. •At the first step, Pd@Mg0.65Sc0.35 decomposes into ScH{sub 2} and MgH{sub 2} under hydrogen pressure (1 MPa) at 330 °C. •The mixture, after decomposition absorbs hydrogen reversibly on Mg/MgH{sub 2} couple with good kinetics. -- Abstract: The deposition of Pd nanoparticles on the binary compound Mg{sub 0.65}Sc{sub 0.35} using the SupercriticalFluid Chemical Deposition (SFCD) method was performed. There, the SFCD operating parameters (co-solvent, temperature, CO{sub 2} and hydrogen pressure, reaction time) have been optimized to obtain homogeneous deposition of Pd nanoparticles (around 10 nm). The hydrogenation properties of the optimized Pd@Mg{sub 0.65}Sc{sub 0.35} material were determined and compared to those of Mg{sub 0.65}Sc{sub 0.35}Pd{sub 0.024}. The latter compound forms at 300 °C and 1 MPa of H{sub 2} a hydride that crystallizes in the fluorite structure, absorbs reversibly 1.5 wt.% hydrogen and exhibits fast kinetics. In contrast, Pd@Mg{sub 0.65}Sc{sub 0.35} compound decomposes into ScH{sub 2} and MgH{sub 2} during hydrogen absorption under the same conditions. However, reversible sorption reaches 3.3 wt.% of hydrogen while keeping good kinetics. The possible roles of Pd on the hydrogen-induced alloy decomposition are discussed.

Supercriticalfluid technology offers several advantages in preparation of microparticles. These include uniformity in particle size, morphology, and drug distribution without degradation of the product. One of the recent advantages is preparation of porous aerogel carrier with proper aerodynamic properties. In this study, we aimed to prepare chitosan aerogel microparticles using supercriticalfluid (SCF) technology and compare that with microparticles produced by freeze drying (FD). Loading the prepared carriers with a model drug (salbutamol) was also performed. Comparisons of the particle properties and physicochemical characterizations were undertaken by evaluating particle size, density, specific surface area, and porosity. In vitro drug release studies were also investigated. The effect of many variables, such as molecular weight of chitosan oligomers, concentrations of chitosan, and concentrations of tripolyphosphate on the release, were also investigated. Chitosan aerogels were efficiently produced by SCF technology with an average particle size of 10 μm with a tapped density values around 0.12 g/mL, specific surface area (73-103) m(2)/g, and porosity (0.20-0.29) cc/g. Whereas, microparticles produced by FD method were characterized as cryogels with larger particle size (64 microns) with clear cracking at the surface. Sustained release profile was achieved for all prepared microparticles of salbutamol produced by the aforementioned methods as compared with pure drug. The results also demonstrates that chitosan molecular weight, polymer concentration, and tripolyphosphate concentration affected the release profile of salbutamol from the prepared microparticles. In conclusion, SCF technology was able to produce chitosan aerogel microparticles loaded with salbutamol that could be suitable for pulmonary drug delivery system.

Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratory research has been conducted on reactions occurring between minerals in the host rock and the wet supercriticalfluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite

Full Text Available A series of manganese salts (Mn(NO32, MnCl2, MnSO4, and Mn(Ac2 and silicon materials (silica sand, silica sol, and tetraethyl orthosilicate were used to synthesize Mn/Si complexes in supercritical water using a tube reactor. X-ray diffraction (XRD, X-ray photoelectron spectrometer (XPS, transmission electron microscopy (TEM, and scanning electron microscopy (SEM were employed to characterize the structure and morphology of the solid products. It was found that MnO2, Mn2O3, and Mn2SiO4 could be obtained in supercritical water at 673 K in 5 minutes. The roles of both anions of manganese salts and silicon species in the formation of manganese silicon complexes were discussed. The inorganic manganese salt with the oxyacid radical could be easily decomposed to produce MnO2/SiO2 and Mn2O3/SiO2. It is interesting to found that Mn(Ac2 can react with various types of silicon to produce Mn2SiO4. The hydroxyl groups of the SiO2 surface from different silicon sources enhance the reactivity of SiO2.

In this study, a rapid and sensitive ultra-high performance supercriticalfluid chromatography-mass spectrometry (UHPSFC-MS) method has been developed and partially validated for the separation of carotenoids within less than 6 min. Six columns of orthogonal selectivity were examined, and the best separation was obtained by using a 1-aminoanthracene (1-AA) column. The length of polyene chain as well as the number of hydroxyl groups in the structure of the studied carotenoids determines their differences in the physiochemical properties and thus the separation that is achieved on this column. All of the investigated carotenoids were baseline separated with resolution values greater than 1.5. The effects of gradient program, back pressure, and column temperature were studied with respect to chromatographic properties such as retention and selectivity. Electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) were compared in both positive and negative mode, using both direct infusion and hyphenated with UHPSFC. The ESI in positive mode provided the highest response. The coefficient of determination (R (2)) for all calibration curves were greater than 0.998. Limit of detection (LOD) was in the range of 2.6 and 25.2 ng/mL for α-carotene and astaxanthin, respectively, whereas limit of quantification (LOQ) was in the range of 7.8 and 58.0 ng/mL for α-carotene and astaxanthin, respectively. Repeatability and intermediate precision of the developed UHPSFC-MS method were determined and found to be RSD supercriticalfluid extracts of microalgae and rosehip. Graphical Abstract Ultra-high performance supercriticalfluid chromatography-a rapid separation method for the analysis of carotenoids in rosehip and microalgae samples.

The development of chemical recycling of waste plastics by decomposition reactions in sub- and supercritical water is reviewed. Decomposition reactions proceed rapidly and selectively using supercriticalfluids compared to conventional processes. Condensation polymerization plastics such as PET, nylon, and polyurethane, are relatively easily depolymerized to their monomers in supercritical water. The monomer components are recovered in high yield. Addition polymerization plastics such as phenol resin, epoxy resin, and polyethylene, are also decomposed to monomer components with or without catalysts. Recycling process of fiber reinforced plastics has been studied. Pilot scale or commercial scale plants have been developed and are operating with sub- and supercriticalfluids.

Gastric acidity is the main factor affecting viability of probiotics in the gastrointestinal tract (GIT). This study investigated the survival in simulated gastrointestinal fluids of Bifidobacterium longum Bb-46 encapsulated in interpolymer complexes formed in supercritical carbon dioxide (scCO(2)). Bacteria were exposed sequentially to simulated gastric fluid (SGF, pH 2) for 2 h and simulated intestinal fluid (SIF, pH 6.8) for 6 or 24 h. Total encapsulated bacteria were determined by suspending 1 g of product in SIF for 6 h at 37 degrees C prior to plating out. Plates were incubated anaerobically at 37 degrees C for 72 h. The interpolymer complex displayed pH-responsive release properties, with little to no release in SGF and substantial release in SIF. There was a limited reduction in viable counts at the end of exposure period due to encapsulation. Protection efficiency of the interpolymer complex was improved by addition of glyceryl monostearate (GMS). Gelatine capsules delayed release of bacteria from the interpolymer complex thus minimizing time of exposure to the detrimental conditions. Use of poly(caprolactone) (PCL), ethylene oxide-propylene oxide triblock copolymer (PEO-PPO-PEO) decreased the protection efficiency of the matrix. Interpolymer complex encapsulation showed potential for protection of probiotics and therefore for application in food and pharmaceuticals.

We investigate a gasdynamic approach to the modeling of heat-release-induced compression waves in supercriticalfluids. We rely on highly resolved one-dimensional fully compressible Navier-Stokes simulations of CO2 at pseudo-boiling conditions in a closed duct inspired by the experiments of Miura et al.. Near-critical fluids exhibit anomalous variations of thermodynamic variables taken into account by adopting the Peng-Robinson equation of state and Chung's Method. An idealized heat source is applied, away from the boundaries, resulting in the generation of compression waves followed by contact discontinuities bounding a region of hot expanding fluid. For higher heat-release rates such compressions are coalescent with distinct shock-like features (i.e. non-isentropicity and propagation Mach numbers measurably greater than unity) and a non-uniform post-shock state, not present in ideal gas simulations, caused by the highly nonlinear equation of state. Thermoacoustic effects are limited to: (1) a one-way/one-time thermal-to-acoustic energy conversion, and (2) cumulative non-isentropic bulk heating due to the resonating compression waves, resulting in what is commonly referred to as the Piston Effect.

This paper proposes the development of an engineered interface between a geopressured-geothermal resource and a supercritical water oxidation (SCWO) process which destroys hazardous organic wastes. The objectives of this study are to show economic advantages in linking the geopressured-geothermal resource with an SCWO process: to destroy hazardous organic waste; to produce power with the combined energy content of the geopressured-geothermal resource and the SCWO process; to use the available energy of the combined system to operate other synergistic processes. The interface will produce a standardized working medium from the hot geopressured-geothermal brine exiting a well, providing hydraulic and thermal energy for operation of the SCWO process. The Department of Energy (DOE) Geopressured-Geothermal Program has been researching the technical and production characteristics of the geopressured-geothermal resource. Three DOE well operations are presently a part of this program. The focus of this study is the development of concepts using a SCWO process to detoxify pollutants at a DOE geopressured-geothermal well site. The existence of large geopressured-geothermal regions throughout the world extends the applicability of the proposed system to many other potential locations in the US and foreign countries. 13 refs., 5 figs.

The chiral separation of d- and l- FMOC amino acids was undertaken using the Lux Cellulose-1 polysaccharide based chiral column in HPLC (normal phase and reverse phase) and SFC conditions. This was done to compare the relative selectivity and separation between the three separation modes and to evaluate the potential benefits of SFC separations with regards to resolution, throughput, economic and environmental impact. It was established that the separation of d- and l- FMOC amino acids in SFC displayed behaviours that were similar to both normal phase and reversed phase, rather than distinctly one or the other. Additionally, although reversed phase conditions yielded significantly higher resolution values between enantiomers across the range of amino acids studied, improvements in selectivity in SFC via the introduction of higher concentrations of formic acid in the mobile phase allowed for better resolution per unit of time. Moreover since the SFC mobile phase is composed mostly of recyclable CO2, there is a reduction in organic solvent consumption, which minimises the economic and environmental costs.

The anti-Trichomonas vaginalis activity of Hypericum polyanthemum extract obtained by supercriticalfluid extraction (50°C, 150bar) and the chemical compounds isolated and purified from this extract (benzopyrans HP1, HP2, HP3, and phloroglucinol derivative uliginosin B) were assessed. All samples had anti-T. vaginalis activity; however, HP1 demonstrated the best selectivity against this protozoan (metronidazole-resistant and susceptible isolates), with no cytotoxicity on mammalian cells (selectivity index of 73.97). Moreover, HP1 had activity against a metronidazole-resistant isolate (52% of viable trophozoites), and this effect was higher when tested with a low concentration of metronidazole (23% of viable trophozoites). Experiments demonstrated that all isolated compounds caused damage to the parasites' membrane (>90% of LDH release) and do not present a notable hemolytic effect, although HP2 and uliginosin B exhibited cytotoxicity against mammalian cells. Therefore, the analyzed molecules are promising prototypes for new antiprotozoal drugs, especially HP1, which seems to improve metronidazole's effect on a resistant T. vaginalis isolate.

A method for supercriticalfluid extraction (SFE) of amino acids was adapted and optimal experimental conditions were selected for a matrix consisting of dry leaves. The matrix-dependent SFE method uses a mixture of MeOH-H(2)O-acetonitrile (10:10:1 v/v/v) as a modifier (0.5 mL in situ, 300 muL on-line) at 70 degrees C and 40 MPa and no HCl is needed as an entrainer. The amino acids were quantified using high-performance liquid chromatography with fluorimetric detection (HPLC/FLD) after gradient elution on Zorbax Eclipse AAA columns (4.6x150 mm, 3.5 mum) with aqueous Na(2)HPO(4 )buffer of pH 7.8 and ACN-MeOH-water as a mobile phase. In comparison with Soxhlet extraction, SFE gave higher recovery and selectivity, but it required longer extraction time (90 min) and it was more labor-intensive (clean-up step after the pre-concentration). Both methods should be used separately or in combination according to the matrix, number of samples, and levels of ballast compounds.

A numerical tool for the simulation of the thermal dynamics of pipe networks with heat transfer has been developed with the novel capability of modeling supercriticalfluids. The tool was developed to support the design and deployment of two thermal-hydraulic loops at Carleton University for the purpose of heat transfer studies in supercritical and near-critical fluids. First, the system was characterized based on its defining features; the characteristic length of the flow path is orders of magnitude larger than the other characteristic lengths that define the system's geometry; the behaviour of the working fluid in the supercritical thermodynamic state. An analysis of the transient thermal behaviour of the model's domains is then performed to determine the accuracy and range of validity of the modeling approach for simulating the transient thermal behaviour of a thermal-hydraulic loop. Preliminary designs of three test section geometries, for the purpose of heat transfer studies, are presented in support of the overall design of the Carleton supercritical thermal-hydraulic loops. A 7-rod-bundle, annular and tubular geometries are developed with support from the new numerical tool. Materials capable of meeting the experimental requirements while operating in supercritical water are determined. The necessary geometries to satisfy the experimental goals are then developed based on the material characteristics and predicted heat transfer behaviour from previous simulation results. An initial safety analysis is performed on the test section designs, where they are evaluated against the ASME Boiler, Pressure Vessel, and Pressure Piping Code standard, required for safe operation and certification.

Full Text Available Several micronization processes based on supercriticalfluids have been developed. These processes can be classified according to the role of the supercriticalfluid in the process: solvent, solute or co-solvent, and anti-solvent. Application of supercriticalfluids as alternative to traditional micronization methods and the growing demand of the industrial sector for new technologies motivated this review. In this context, the objective of this work was to present the operating principles of the micronization process by means of supercriticalfluids and the effects of the main process variables on particles characteristics. The review continues with an update of current experimental data presented in the literature in the period from 2008 to 2012.

This new, recently developed extracting techniqne, SupercriticalFluid Extraction (SFE), features many advantages in natural product extraction, such as a satisfactory rate of extraction, a high isolation effect, and, when operated entirely free of residual solvents, low cost.

Supercriticalfluid extrusion (SCFX) was used to produce shelf-stable puffed rice fortified with protein, dietary fiber, and micronutrients. Product ingredients and process parameters were evaluated for end-product nutritional and textural qualities. Supercritical carbon dioxide (SC-CO(2)) served as a viscosity-lowering plasticizer and blowing agent during the process, which has been shown to produce expanded products with good textural qualities at lower temperatures (~100 °C) than conventional steam-based extrusion (130-180 °C). The fortified puffed rice contained 8% dietary fiber, 21.5% protein, and iron, zinc, and vitamins A and C at their recommended daily values in 100 g of product. The SCFX process allowed for the complete retention of all added minerals, 55-58% retention of vitamin A, and 64-76% retention of vitamin C. All essential amino acids including lysine were retained at exceptionally high levels (98.6%), and no losses were observed due to Maillard reaction or oxidation. All of the essential amino acid contents were equal to the reference protein recommended by FAO/WHO. Soy protein fortification improved the total amount of protein in the final rice products and provided a complementary amino acid profile to that of rice; the lysine content improved from 35 to 60 mg/protein, making the end product an excellent source of complete protein. Thus, SC-CO(2)-assisted extrusion is an effective process-based approach to produce cereal grain-based, low-moisture (5-8%) expanded products fortified with protein and any cocktail of micronutrients, without compromising the end-product sensory or nutritional qualities. These products are ideally suited for consumption as breakfast cereals, snack foods, and as part of nutrition bars for school lunch programs. The balanced nutritional profile and use of staple crop byproducts such as broken rice makes these expanded crisps unique to the marketplace.

Full Text Available Using ammonium bicarbonate (AB particles as a porogen, chitosan (CS-based hemostatic porous sponges were prepared in supercritical carbon dioxide due to its low viscosity, small surface tension, and good compatibility with organic solvent. Fourier transform infrared spectroscopy (FTIR spectra demonstrated that the chemical compositions of CS and poly-(methyl vinyl ether-co-maleic anhydride (PVM/MA were not altered during the phase inversion process. The morphology and structure of the sponge after the supercriticalfluid (SCF process were observed by scanning electron microscopy (SEM. The resulting hemostatic sponges showed a relatively high porosity (about 80% with a controllable pore size ranging from 0.1 to 200 µm. The concentration of PVM/MA had no significant influence on the porosity of the sponges. Comparative experiments on biological assessment and hemostatic effect between the resulting sponges and Avitene® were also carried out. With the incorporation of PVM/MA into the CS-based sponges, the water absorption rate of the sponges increased significantly, and the CS-PVM/MA sponges showed a similar water absorption rate (about 90% to that of Avitene®. The results of the whole blood clotting experiment and animal experiment also demonstrated that the clotting ability of the CS-PVM/MA sponges was similar to that of Avitene®. All these results elementarily verified that the sponges prepared in this study were suitable for hemostasis and demonstrated the feasibility of using SCF-assisted phase inversion technology to produce hemostatic porous sponges.

Full Text Available Nonlinear vibration of a fluid-conveying pipe subjected to a transverse external harmonic excitation is investigated in the case with two-to-one internal resonance. The excitation amplitude is in the same magnitude of the transverse displacement. The fluid in the pipes flows in the speed larger than the critical speed so that the straight configuration becomes an unstable equilibrium and two curved configurations bifurcate as stable equilibriums. The motion measured from each of curved equilibrium configurations is governed by a nonlinear integro-partial-differential equation with variable coefficients. The Galerkin method is employed to discretize the governing equation into a gyroscopic system consisting of a set of coupled nonlinear ordinary differential equations. The method of multiple scales is applied to analyze approximately the gyroscopic system. A set of first-order ordinary differential equations governing the modulations of the amplitude and the phase are derived via the method. In the supercritical regime, the subharmonic, superharmonic, and combination resonances are examined in the presence of the 2 : 1 internal resonance. The steady-state responses and their stabilities are determined. The various jump phenomena in the amplitude-frequency response curves are demonstrated. The effects of the viscosity, the excitation amplitude, the nonlinearity, and the flow speed are observed. The analytical results are supported by the numerical integration.

Highlights: • Understanding of the mechanism of buoyancy effect on supercritical heat transfer. • Turbulence related parameters in upward and downward flows were compared. • Turbulent Prandtl number affected the prediction insignificantly. • Buoyancy production was insignificant compared with shear production. • Damping function had the greatest effect and is a priority for further modification. - Abstract: Heat transfer to supercritical pressure fluids was modeled for normal and buoyancy affected conditions using several low Reynolds number k-ε models, including the Launder and Sharma, Myong and Kasagi, and Abe, Kondoh and Nagano, with the predictions compared with experimental data. All three turbulence models accurately predicted the cases without heat transfer deterioration, but failed to accurately predict the cases with heat transfer deterioration although the general trends were captured, indicating that further improvements and modifications are needed for the low Reynolds number k-ε turbulence models to better predict buoyancy deteriorated heat transfer. Further investigations studied the influence of various aspects of the low Reynolds number k-ε turbulence models, including the turbulent Prandtl number, the buoyancy production of turbulent kinetic energy, and the damping function to provide guidelines for model development to more precisely predict buoyancy affected heat transfer. The results show that the turbulent Prandtl number and the buoyancy production of turbulent kinetic energy have little influence on the predictions for cases in this study, while new damping functions with carefully selected control parameters are needed in the low Reynolds number k-ε turbulence models to correctly predict the buoyancy effect for heat transfer simulations in various applications such as supercritical pressure steam generators (SPSGs) in the high temperature gas cooled reactor (HTR) and the supercritical pressure water reactor (SCWR).

Under contract from the DOE , and in association with CONSOL Inc., Battelle, Pacific Northwest Laboratory (PNL) evaluated four principal and several complementary techniques for the analysis of non-distillable direct coal liquefaction materials in support of process development. Field desorption mass spectrometry (FDMS) and nuclear magnetic resonance (NMR) spectroscopic methods were examined for potential usefulness as techniques to elucidate the chemical structure of residual (nondistillable) direct coal liquefaction derived materials. Supercriticalfluid extraction (SFE) and supercriticalfluid chromatography/mass spectrometry (SFC/MS) were evaluated for effectiveness in compound-class separation and identification of residual materials. Liquid chromatography (including microcolumn) separation techniques, gas chromatography/mass spectrometry (GC/MS), mass spectrometry/mass spectrometry (MS/MS), and GC/Fourier transform infrared (FTIR) spectroscopy methods were applied to supercriticalfluid extracts. The full report authored by the PNL researchers is presented here. The following assessment briefly highlights the major findings of the project, and evaluates the potential of the methods for application to coal liquefaction materials. These results will be incorporated by CONSOL into a general overview of the application of novel analytical techniques to coal-derived materials at the conclusion of CONSOL`s contract.

The direct asymmetric aldol reaction between various aldehydes and acetone catalyzed by L-proline catalyst was successfully carried out in supercritical CO2 (scCO2) and 1,1,1,2-tetrafluoroethane (R-134a) fluids.The enantioselectivity of 84% ee to the targeted product was achieved under 20 MPa,40 °C,and 15 mol% of the catalyst in supercritical CO2 (scCO2) fluid.The effects of reaction parameters,such as temperature,pressure,catalyst loading and different substituted aldehydes on both enantioselectivity and aldol yield were discussed.The titled reaction was also performed in 1,1,1,2-tetrafluoroethane,and the obtained results were compared with those in scCO2.This new reaction procedure provides an environmental asymmetric aldol reaction system as compared with that in organic solvents.

A synergistic supercritical extraction process was developed and its feasibility demonstrated using a semi-batch extraction process unit. The process was found to be effective in selectively cleaning organic sulfur from Ohio coals. Optimal case involved a mixture of CO{sub 2}, H{sub 2}O, and CH{sub 3}OH, and the removal of organic sulfur ranged from 35 to 55%. Combined with pyrite and mineral matter removal by gravity, the resulting coals would have 20--30% increased heating values and SO{sub 2} emissions would be down to 1.2--1.5 pounds per million Btu, thus meeting compliance requirements. Estimated cleaning cost including pyrite removal is $25 to 45 per ton. The most important cost factor is the operation at high pressures.

A synergistic supercritical extraction process was developed and its feasibility demonstrated using a semi-batch extraction process unit. The process was found to be effective in selectively cleaning organic sulfur from Ohio coals. Optimal case involved a mixture of CO{sub 2}, H{sub 2}O, and CH{sub 3}OH, and the removal of organic sulfur ranged from 35 to 55%. Combined with pyrite and mineral matter removal by gravity, the resulting coals would have 20--30% increased heating values and SO{sub 2} emissions would be down to 1.2--1.5 pounds per million Btu, thus meeting compliance requirements. Estimated cleaning cost including pyrite removal is $25 to 45 per ton. The most important cost factor is the operation at high pressures.

Full Text Available Supercritical carbon dioxide extraction, as a relatively new separation technique, can be used as a very efficient process in the production of essential oils and oleoresins from many of plant materials. The extracts from these materials are a good basis for the new pharmaceutical products and ingredients in the functional foods. This paper deals with supercritical carbon dioxide extraction of selected oil seeds which are of little interest in classical extraction in the food industry. In this article the process parameters in the supercritical carbon dioxide extraction, such as pressure, temperature, solvent flow rate, diameter of gound materials, and moisture of oil seed were presented for the following seeds: almond fruits, borage seed, corn germ, grape seed, evening primrose, hazelnut, linseed, pumpkin seed, walnut, and wheat germ. The values of investigated parameters in supercritical extraction were: pressure from 100 to 600 bar, temperature from 10 to 70oC, diameter of grinding material from 0.16 to 2.0 mm, solvent flow used from 0.06 to 30.0 kg/h, amount of oil in the feed from 10.0 to 74.0%, and moisture of oil seed from 1.1 to 7.5%. The yield and quality of the extracts of all the oil seeds as well as the possibility of their application in the pharmaceutical and food, industries were analyzed.

We propose an approximation of a direct correlation function corresponding to the linearization with respect to - βϕ( r) of a generalized mean spherical approximation for a hard-core multi-Yukawa system of particles. We use the results to study the behavior of maximums of thermodynamic response functions in the supercritical region of a fluid with a two-term Yukawa potential imitating the Lennard-Jones potential.

With the global drive for faster, more environmentally friendly separation techniques, the aim of this research was to demonstrate the potential of SupercriticalFluid Chromatography (SFC) as a viable alternative or complementary technique to High Performance Liquid Chromatography (HPLC) in the highly regulated world of the Quality Control (QC) laboratory. SFC methods capable of meeting QC method performance expectations in accordance with current guidance were therefore developed and v...

The consumer trend for healthier food choices and preferences for low-fat products has increased the interest in low-fat cheese and nutraceutical dairy products. However, consumer preference is still for delicious food. Low- and reduced-fat cheeses are not completely accepted because of their unappealing properties compared with full-fat cheeses. The method reported here provides another option to the conventional cheese-making process to obtain lower fat cheese. Using CO(2) as a supercriticalfluid offers an alternative to reduce fat in cheese after ripening, while maintaining the initial characteristics and flavor. The aim of this experiment was to evaluate the effect of pressure (10, 20, 30, and 40 × 10(6) Pa) of supercritical CO(2) on the amount of fat extracted, microbial population, polar lipid profile, and microstructure of 2 varieties of goat cheese: Majorero, a protected denomination of origin cheese from Spain, and goat Gouda-type cheese. The amount of fat was reduced 50 to 57% and 48 to 55% for Majorero and goat Gouda-type cheeses, respectively. Higher contents (on a fat basis) of sphingomyelin and phosphatidylcholine were found in Majorero cheese compared with control and goat Gouda-type cheeses. The microbial population was reduced after supercriticalfluid extraction in both cheeses, and the lethality was higher as pressure increased in Majorero cheese, most noticeably on lactococcus and lactobacillus bacteria. The Gouda-type cheese did not contain any lactobacilli. Micrographs obtained from confocal laser scanning microscopy showed a more open matrix and whey pockets in the Majorero control cheese. This could explain the ease of extracting fat and reducing the microbial counts in this cheese after treatment with supercritical CO(2). Supercriticalfluid extraction with CO(2) has great potential in the dairy industry and in commercial applications. The Majorero cheese obtained after the supercriticalfluid extraction treatment was an excellent

Syzygium campanulatum Korth is a plant, which is a rich source of secondary metabolites (especially flavanones, chalcone, and triterpenoids). In our present study, three conventional solvent extraction (CSE) techniques and supercriticalfluid extraction (SFE) techniques were performed to achieve a maximum recovery of two flavanones, chalcone, and two triterpenoids from S. campanulatum leaves. Furthermore, a Box-Behnken design was constructed for the SFE technique using pressure, temperature, and particle size as independent variables, and yields of crude extract, individual and total secondary metabolites as the dependent variables. In the CSE procedure, twenty extracts were produced using ten different solvents and three techniques (maceration, soxhletion, and reflux). An enriched extract of five secondary metabolites was collected using n-hexane:methanol (1:1) soxhletion. Using food-grade ethanol as a modifier, the SFE methods produced a higher recovery (25.5%‒84.9%) of selected secondary metabolites as compared to the CSE techniques (0.92%‒66.00%). PMID:27604860

Atmospheric-pressure laser ionization mass spectrometry (APLI-MS) is a powerful method for the analysis of polycyclic aromatic hydrocarbon (PAH) molecules, which are ionized in a selective and highly sensitive way via resonance-enhanced multiphoton ionization. APLI was presented in 2005 and has been hyphenated successfully to chromatographic separation techniques like high performance liquid chromatography (HPLC) and gas chromatography (GC). In order to expand the portfolio of chromatographic couplings to APLI, a new hyphenation setup of APLI and supercritical-fluid chromatography (SFC) was constructed and aim of this work. Here, we demonstrate the first hyphenation of SFC and APLI in a simple designed way with respect to different optimization steps to ensure a sensitive analysis. The new setup permits qualitative and quantitative determination of native and also more polar PAH molecules. As a result of the altered ambient characteristics within the source enclosure, the quantification of 1-hydroxypyrene (1-HP) in human urine is possible without prior derivatization. The limit of detection for 1-HP by SFC-APLI-TOF(MS) was found to be 0.5 μg L(-1), which is lower than the 1-HP concentrations found in exposed persons.

A case of elution order inversion caused by cosolvent percentage change in supercriticalfluid chromatography was observed and investigated in some detail. Z- and E-isomers of phenylisobutylketone oxime experience an elution order reversal on most columns if the mobile phase consists of CO2 and alcohol. At lower percentages of alcohol Z-oxime is retained less, somewhere at 2-5% coelution occurs and at larger cosolvent volume elution order reverses - Z-oxime is eluted later than E-oxime. We suppose inversion with CO2-ROH phases happens due to a shift in balance between two main interactions governing retention. At low ROH percentages stationary phase surface is only slightly covered by ROH molecules so oximes primarily interact with adsorption sites via hydrogen bond formation. Due to intramolecular sterical hindrance Z-oxime is less able to form hydrogen bonds and consequently is eluted first. At higher percentages alcohols occupy most of strong hydrogen bonding sites on silica surface thus leaving non-specific electrostatic interactions predominantly responsible for Z/E selectivity. Z-oxime has a much larger dipole moment than E-oxime and at these conditions it is eluted later. Additional experimental data with CO2-CH3CN, hexane-iPrOH and CHF3-ROH mobile phases supporting this explanation are presented.

While the number and diversity of lead compounds has increased with the development of science technologies, ca. 90 % of new chemical entities under development have shown low aqueous solubility, classified as class II or IV of the biopharmaceutics classification system (BCS). The low aqueous solubility hinders their clinical translations due to low bioavailability and dissolution-limited absorption of orally-administered drugs. Several technologies have been employed to improve the solubility of poorly water-soluble drugs. In this paper, a new method of nanoparticulation using fat and a supercriticalfluid (NUFS) for the formulation of hydrophobic drugs was applied to solve the low solubility problem. A typical BCS class II drug, itraconazole, was selected and formulated with hydroxypropyl methylcellulose, emulsification, and anticoagulating agents for NUFS. The non-spherical itraconazole nanoparticles prepared by NUFS were ~300-500 nm in size with a ~15-fold improved dissolution rate compared to non-nanoparticles of itraconazole (i.e., raw itraconazole). In addition, a high drug content of ~46 % by weight and a drug loading efficiency greater than 85 % were achieved. Therefore, the new technology for nano-platforms could be a promising solution for solubilization of poorly water-soluble drugs, resulting in improved bioavailability.

Traditional chromatographic methods for the analysis of lignin-derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra-high performance supercriticalfluid chromatography method with a diode array detector for the analysis of major lignin-derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5-2.5 μM, a limit of quantification of 2.5-5.0 μM, and a dynamic range of 5.0-2.0 mM (R(2) > 0.997). The new ultra-high performance supercriticalfluid chromatography method was also applied for the qualitative and quantitative analysis of lignin-derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercriticalfluid chromatography is a fast and reliable technique for the analysis of lignin-derived phenols in complex environmental samples.

Full Text Available Abstract In order to take full advantage of Tenebrio molitor larvae (yellow mealworm resources, the supercritical CO2 fluid freeze-dried powder of T. molitor larvae (fdTML extraction on the immune systems of mice was carried out. The results about the effects of supercritical CO2 fluid fdTML extraction on carbon expurgation and phagocytosis of peritoneal macrophages experiments of mice indicated that the fdTML extraction enhanced observably carbon expurgatory index, phagocytic rate and phagocytic index. The fdTML extraction could stimulate response of delayed hypersensitivity. The proliferation of ConA-induced mitogenic reponse for spleen lymphocyte was also increased. The amount of hemolytic antibody in mice serum increased compared with those of the control group mice. The half of hemolysis values in serum of treated mice increased compared to the control group. Furthermore, serum NO content in all treatment groups was higher than that of the control group whereas acid phosphatase and alkaline phosphatase activity was only significantly higher relative to the control group. Our findings suggest that supercritical CO2 fluid the fdTML extraction has potential as a health food supplement.

The separation method using chiral stationary phase (CSP) for the preparation of enantioselective compound was widely used. In this work, supercriticalfluid chromatography(SFC) was proposed to resolve the chiral mixtures. To determine the optimum operating conditions for the chiral separation of the racemic ibuprofen,the retention factors and resolutions with the change in pressure, temperature and the content of IPA (%, by volume)in supercritical CO2 were investigated. Experiments showed that the retention factor decreased with the increase of pressure and decrease in temperature. The retention factor was also influenced by the content of IPA in mobile phase, as the content of IPA in the supercriticalfluid increased, the retention factor decreased. The resolution of the enantiomers became worse with the increase of IPA in the supercriticalfluid. Through optimizing the experimental conditions, a SFC procedure with 13MPa, 311.15K and 4% IPA in CO2 was obtained. The peak shape of the enantiomers was symmetric with supercriticalfluid chromatography when compared to the asymmetric peak shape obtained by the conventional liquid chromatography. This work demonstrated that the developed supercriticalfluid chromatography procedure was suitable for the chiral separation of ibuprofen enantiomers.

The transport of immiscible fluids within porous media is a topic of great importance for a wide range of subsurface processes; e.g. oil recovery, geologic sequestration of CO2, gas-water mass transfer in the vadose zone, and remediation of non-aqueous phase liquids (NAPLs) from groundwater. In particular, the trapping and mobilization of nonwetting phase fluids (e.g. oil, CO2, gas, or NAPL in water-wet media) is of significant concern; and has been well documented to be a function of both wetting and nonwetting fluid properties, morphological characteristics of the porous medium, and system history. However, generalization of empirical trends and results for application between different fluid-fluid-medium systems requires careful consideration and characterization of the relevant system properties. We present a comprehensive and cohesive description of nonwetting phase behaviour as observed via a suite of three dimensional x-ray microtomography imaging experiments investigating immiscible fluid flow, trapping, and interfacial interactions of wetting (brine) and nonwetting (air, oil, and supercritical CO2) phase in sandstones and synthetic media. Microtomographic images, acquired for drainage and imbibition flow processes, allow for precise and extensive characterization of nonwetting phase fluid saturation, topology, and connectivity; imaging results are paired with externally measured capillary pressure data to provide a comprehensive description of fluid states. Fluid flow and nonwetting phase trapping behaviour is investigated as a function of system history, morphological metrics of the geologic media, and nonwetting phase fluid characteristics; and particular emphasis is devoted to the differences between ambient condition (air-brine) and reservoir condition (supercritical CO2-brine) studies. Preliminary results provide insight into the applicability of using ambient condition experiments to explore reservoir condition processes, and also elucidate the

For several decades, heterogeneous catalytic processes have been improved through utilizing supercriticalfluids (SCFs) as solvents. While numerous experimental studies have been established across a range of chemistries, such as oxidation, pyrolysis, amination, and Fischer-Tropsch synthesis, still there is little fundamental, molecular-level information regarding the role of the SCF on elementary heterogeneous catalytic steps. In this study, the influence of hexane solvent on the adsorption of carbon monoxide on Co(0001), as the first step in the reaction mechanism of many processes involving syngas conversion, is probed. Simulations are performed at various bulk hexane densities, ranging from ideal gas conditions (no SCF hexane) to various near- and super-critical hexane densities. For this purpose, both density functional theory and molecular dynamics simulations are employed to determine the adsorption energy and free energy change during CO chemisorption. Potential of mean force calculations, utilizing umbrella sampling and the weighted histogram analysis method, provide the first commentary on SCF solvent effects on the energetic aspects of the chemisorption process. Simulation results indicate an enhanced stability of CO adsorption on the catalyst surface in the presence of supercritical hexane within the reduced pressure range of 1.0-1.5 at a constant temperature of 523 K. Furthermore, it is shown that the maximum stability of CO in the adsorbed state as a function of supercritical hexane density at 523 K nearly coincides with the maximum isothermal compressibility of bulk hexane at this temperature.

Full Text Available Plants belonging to the genus Salvia (Lamiaceae are known to have a wide range of biological properties. In this work, extracts obtained from the aerial parts of Salvia sclareoides Brot. were evaluated to investigate their chemical composition, toxicity, bioactivity, and stability under in vitro gastrointestinal conditions. The composition of the supercriticalfluid extract was determined by GC and GC-MS, while the identification of the infusion constituents was performed by HPLC-DAD and LC-MS. The in vitro cytotoxicity of both extracts (0-2 mg/mL was evaluated in Caco-2 cell lines by the MTT assay. The anti-inflammatory and anticholinesterase activities were determined through the inhibition of cyclooxygenase-1 and acetylcholinesterase enzymes, while β-carotene/linoleic acid bleaching test and the DPPH assays were used to evaluate the antioxidant activity. The infusion inhibited cyclooxygenase-1 (IC50 = 271.0 μg/mL, and acetylcholinesterase (IC50 = 487.7 μg/ mL enzymes, also demonstrated significant antioxidant properties, as evaluated by the DPPH (IC50 = 10.4 μg/mL and β-carotene/linoleic acid (IC50 = 30.0 μg/mL assays. No remarkable alterations in the composition or in the bioactivities of the infusion were observed after in vitro digestion, which supports the potential of S. sclareoides as a source of bioactive ingredients with neuroprotective, anti-inflammatory and antioxidant properties.

We have performed extensive molecular dynamics simulations to study noise-power spectra of density and potential energy fluctuations of a Lennard-Jones model of a fluid in the supercritical region. Emanating from the liquid-vapor critical point, there is a locus of isobaric specific heat maxima, called the Widom line, which is often regarded as an extension of the liquid-vapor coexistence line. Our simulation results show that the noise-power spectrum of the density fluctuations on the Widom line of the liquid-vapor transition exhibits three distinct 1/f^{γ} behaviors with exponents γ=0, 1.2, and 2, depending on the frequency f. We find that the intermediate frequency region with an exponent γ∼ 1 appears as the temperature approaches the Widom temperature from above or below. On the other hand, we do not find three distinct regions of 1/f^{γ} in the power spectrum of the potential energy fluctuations on the Widom line. Furthermore, we find that the power spectra of both the density and potential energy fluctuations at low frequency have a maximum on the Widom line, suggesting that the noise power can provide an alternative signature of the Widom line.

A study was made of the conversion of single spherical coal particles of diameter 1-5 mm in a supercritical H{sub 2}O/O{sub 2} fluid with an oxygen mass fraction of 0-6.6% in a semibatch reactor at a pressure of 30 MPa and a temperature of 673-1023 K. A decrease in the particle mass was observed in two parallel processes: gasification of coal with water and oxidation of coal with oxygen. An activation energy 19 {+-} 7 kJ/mole and a pre-exponential factor 10{sup -2}{+-} 0.4 sec{sup -1} were obtained under the assumption of zero order for the concentration H{sub 2}O and an Arrhenius dependence for the rate of gasification with water. The oxidation with oxygen at a temperature above 780 K was found to be limited by the rate of O{sub 2} diffusion to the coal organic matter. Below 780 K, the rate of heterogeneous oxidation with oxygen is described by a first-order reaction for the concentration of O{sub 2} and a zero-order reaction for the concentration of H{sub 2}O with an activation energy of 150 {+-} 27 kJ/mole and a pre-exponential factor of 10{sup 7.6}{+-} 1.9 cm{sup 3}/(g . sec).

Full Text Available Supercriticalfluid extraction (SFE was used to extract quinones from compost to monitor the microbial community dynamics during composting. The 0.3 g of dried compost was extracted using 3 mL min−1 of carbon dioxide (90% and methanol (10% at 45°C and 25 MPa for a 30 min extraction time. The extracted quinones were analysed using ultra performance liquid chromatography (UPLC with 0.3 mL min−1 of methanol mobile phase for a 50 min chromatographic run time. A comparable detected amount of quinones was obtained using the developed method and an organic solvent extraction method, being 36.06 μmol kg−1 and 34.54 μmol kg−1, respectively. Significantly low value of dissimilarity index (D between the two methods (0.05 indicated that the quinone profile obtained by both methods was considered identical. The developed method was then applied to determine the maturity of the compost by monitoring the change of quinone during composting. The UQ-9 and MK-7 were predominant quinones in the initial stage of composting. The diversity of quinone became more complex during the cooling and maturation stages. This study showed that SFE had successfully extracted quinones from a complex matrix with simplification and rapidity of the analysis that is beneficial for routine analysis.

Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercriticalfluid solution at an elevated pressure and then rapidly expanding the solution through a heated nozzle having a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. In another embodiment, the temperature of the solution and nozzle is elevated above the melting point of the solute, which is preferably a polymer, and the solution is maintained at a pressure such that, during expansion, the solute precipitates out of solution within the nozzle in a liquid state. Alternatively, a secondary solvent mutually soluble with the solute and primary solvent and having a higher critical temperature than that of primary solvent is used in a low concentration (<20%) to maintain the solute in a transient liquid state. The solute is discharged in the form of long, thin fibers. The fibers are collected at sufficient distance from the orifice to allow them to solidify in the low pressure/temperature region.

Supercriticalfluid extraction (SFE) of the volatile oil from Thymus vulgaris L. aerial flowering parts was performed under different conditions of pressure, temperature, mean particle size and CO(2) flow rate and the correspondent yield and composition were compared with those of the essential oil isolated by hydrodistillation (HD). Both the oils were analyzed by GC and GC-MS and 52 components were identified. The main volatile components obtained were p-cymene (10.0-42.6% for SFE and 28.9-34.8% for HD), gamma-terpinene (0.8-6.9% for SFE and 5.1-7.0% for HD), linalool (2.3-5.3% for SFE and 2.8-3.1% for HD), thymol (19.5-40.8% for SFE and 35.4-41.6% for HD), and carvacrol (1.4-3.1% for SFE and 2.6-3.1% for HD). The main difference was found to be the relative percentage of thymoquinone (not found in the essential oil) and carvacryl methyl ether (1.0-1.2% for HD versus t-0.4 for SFE) which can explain the higher antioxidant activity, assessed by Rancimat test, of the SFE volatiles when compared with HD. Thymoquinone is considered a strong antioxidant compound.

Stainless steel (SS) particles were demonstrated as a novel useful support for a water stationary phase in packed column supercriticalfluid chromatography using a CO2 mobile phase. Separations employed flame ionization detection, and the system was operated over a range of temperatures and pressures. Retention times reproduced well with RSD values of 2.6% or less. Compared to analogous separations employing a water stationary phase coated onto a SS capillary column, the packed column method provided separations that were about 10× faster, with nearly 8-fold larger analyte retention factors, while maintaining good peak shape and comparable column efficiency. Under normal operating conditions, the packed column contains about 131 ± 4 μL/m of water phase (around a 5% m/m coating), which is over 25× greater than the capillary column and also affords it a 20-fold larger sample capacity. Several applications of the packed column system are examined, and the results indicate that it is a useful alternative to the capillary column mode, particularly where analyte loads or sample matrix interference is a concern. Given its high sample capacity, this packed column method may also be useful to explore on a more preparative scale in the future.

Full Text Available Examination of organic pollutants in groundwaters should also consider the source of the pollution, which is often a solid matrix such as soil, landfill waste, or sediment. This premise should be viewed alongside the growing trend towards field-based characterisation of contaminated sites for reasons of speed and cost. Field-based methods for the extraction of organic compounds from solid samples are generally cumbersome, time consuming, or inefficient. This paper describes the development of a field-based supercriticalfluid extraction (SFE system for the recovery of organic contaminants (benzene, toluene, ethylbenzene, and xylene and polynuclear aromatic hydrocarbons from soils. A simple, compact, and robust SFE system has been constructed and was found to offer the same extraction efficiency as a well-established laboratory SFE system. Extraction optimisation was statistically evaluated using a factorial analysis procedure. Under optimised conditions, the device yielded recovery efficiencies of >70% with RSD values of 4% against the standard EPA Soxhlet method, compared with a mean recovery efficiency of 48% for a commercially available field-extraction kit. The device will next be evaluated with real samples prior to field deployment.

An offline supercriticalfluid extraction (SFE) method has been developed to determine PCB congeners and total tissue lipid content in edible fish and crab tissues collected from several river systems in Virginia. The method is rapid and safe, requiring only 40 minutes per sample and uses nonorganic solvents for total lipid extraction and only 1.5 mL isooctane for PCB extraction. The SFE approach compares favorably with soxhlet extraction, ASE and column elution. Over 800 fish and crab tissue samples were analyzed successfully, thus demonstrating the robustness of the method. Total lipid values obtained using SFE showed considerable spatial and interspecies variability ranging from 1.8% in blue crab (Callinectes sapidus) to 36.4% in striped bass (Morone saxatilis). Total PCB concentrations also varied greatly by site and species. These ranged from below the quantitation limit (1.0 {micro}1 g/kg) to 9,910 {micro}g/kg on a dry weight basis using GCELCD. Dominant PCB congeners detected were in good agreement with those reported by other researchers. Mean total PCB concentrations did not correlate well with total tissue lipid content.

Supercriticalfluid chromatography (SFC) has gained considerable importance in the area of Separation Science in pharmaceutical analysis over the past few years. The synthesis of chiral compounds is of particular significance in the pursuit of new drug entities. SFC is rapidly replacing high performance liquid chromatography (HPLC) in many pharmaceutical and biotechnological companies as the standard screening and method development tool for chiral compounds. Analysis of pharmaceutical formulations of research compounds is an area where SFC is recently being explored as a possible alternate or complementary technique to HPLC in limited scope. A feasibility study was carried out to perform direct assay of a chiral drug compound AZM in 100% aqueous formulations by SFC. The results indicated that this approach has the potential to significantly reduce the typical sample processing time prior to analysis. The method was reproducible, linear over a wide dynamic range, and sensitive enough to detect the minor enantiomeric impurity in the chiral drug compound investigated here. Further application will be pursued for other research compounds in the future to illustrate the broader applicability of this approach.

Surface excess adsorption isotherms of methanol on a diol silica adsorbent were measured in supercriticalfluid chromatography (SFC) using a mixture of methanol and carbon dioxide as mobile phase. The tracer pulse method was used with deuterium labeled methanol as solute and the tracer peaks were detected using APCI-MS over the whole composition range from neat carbon dioxide to neat methanol. The results indicate that a monolayer (4Å) of methanol is formed on the stationary phase. Moreover, the importance of using the set or the actual methanol fractions and volumetric flows in SFC was investigated by measuring the mass flow respective pressure and by calculations of the actual volume fraction of methanol. The result revealed a significant difference between the value set and the actually delivered volumetric methanol flow rate, especially at low modifier fractions. If relying only on the set methanol fraction in the calculations, the methanol layer thickness should in this system be highly overestimated. Finally, retention times for a set of solutes were measured and related to the findings summarized above concerning methanol adsorption. A strongly non-linear relationship between the logarithms of the retention factors and the modifier fraction in the mobile phase was revealed, prior to the established monolayer. At modifier fractions above that required for establishment of the methanol monolayer, this relationship turns linear which explains why the solute retention factors are less sensitive to changes in modifier content in this region.

When using compressible mobile phases such as fluidic CO2, the density, the volumetric flow rates and volumetric fractions are pressure dependent. The pressure and temperature definition of these volumetric parameters (referred to as the reference conditions) may alter between systems, manufacturers and operating conditions. A supercriticalfluid chromatography system was modified to operate in two modes with different definition of the eluent delivery parameters, referred to as fixed and variable mode. For the variable mode, the volumetric parameters are defined with reference to the pump operating pressure and actual pump head temperature. These conditions may vary when, e.g. changing the column length, permeability, flow rate, etc. and are thus variable reference conditions. For the fixed mode, the reference conditions were set at 150bar and 30°C, resulting in a mass flow rate and mass fraction of modifier definition which is independent of the operation conditions. For the variable mode, the mass flow rate of carbon dioxide increases with system pump operating pressure, decreasing the fraction of modifier. Comparing the void times and retention factor shows that the deviation between the two modes is almost independent of modifier percentage, but depends on the operating pressure. Recalculating the set volumetric fraction of modifier to the mass fraction results in the same retention behaviour for both modes. This shows that retention in SFC can be best modelled using the mass fraction of modifier. The fixed mode also simplifies method scaling as it only requires matching average column pressure.

A simple and sensitive method for the enantioselective determination of tebuconazole enantiomers in water and zebrafish has been established using supercriticalfluid chromatography (SFC)-MS/MS. The effects of the chiral stationary phases, mobile phase, auto back pressure regulator (ABPR) pressure, column temperature, flow rate of the mobile phase, and compensation pump solvent were evaluated. Finally, the optimal SFC-MS/MS working conditions were determined to include a CO2/MeOH mobile phase (87:13, v/v), 2.0 mL/min flow rate, 2200 psi ABPR, and 30 °C column temperature using a Chiralpak IA-3 chiral column under electrospray ionization positive mode. The modified QuEChERS method was applied to water and zebrafish samples. The mean recoveries for the tebuconazole enantiomers were 79.8-108.4% with RSDs ≤ 7.0% in both matrices. The LOQs ranged from 0.24 to 1.20 μg/kg. The developed analytical method was further validated by application to the analysis of authentic samples.

Supercriticalfluid particle design (SCF PD) offers a number of routes to improve solubility and dissolution rate for enhancing the bioavailability of poorly water-soluble drugs, which can be adopted through an in-depth knowledge of SCF PD processes and the molecular properties of active pharmaceutical ingredients (API) and drug delivery system (DDS). Combining with research experiences in our laboratory, this review focuses on the most recent development of different routes (nano-micron particles, polymorphic particles, composite particles and bio-drug particles) to improve solubility and dissolution rate of poorly water-soluble drugs, covering the fundamental concept of SCF and the principle of SCF PD processes which are typically used to control particle size, shape, morphology and particle form and hence enable notable improvement in the dissolution rate of the poorly water-soluble drugs. The progress of the industrialization of SCF PD processes in pharmaceutical manufacturing environment with scaled-up plant under current good manufacturing process (GMP) specification is also considered in this review.

Although supercriticalfluid chromatography (SFC) is becoming a technique of increasing importance in the field of analytical chromatography, methods to compare the performance of SFC-columns and separations in an unbiased way are not fully developed. The present study uses mathematical models to investigate the possibilities and limitations of the kinetic plot method in SFC as this easily allows to investigate a wide range of operating pressures, retention and mobile phase conditions. The variable column length (L) kinetic plot method was further investigated in this work. Since the pressure history is identical for each measurement, this method gives the true kinetic performance limit in SFC. The deviations of the traditional way of measuring the performance as a function of flow rate (fixed back pressure and column length) and the isopycnic method with respect to this variable column length method were investigated under a wide range of operational conditions. It is found that using the variable L method, extrapolations towards other pressure drops are not valid in SFC (deviation of ∼15% for extrapolation from 50 to 200bar pressure drop). The isopycnic method provides the best prediction but its use is limited when operating closer towards critical point conditions. When an organic modifier is used, the predictions are improved for both methods with respect to the variable L method (e.g. deviations decreases from 20% to 2% when 20mol% of methanol is added).

Milk fat globule membrane contains many complex lipids implicated in an assortment of biological processes. Microfiltration coupled with supercriticalfluid extraction (SFE) has been shown to provide a method of concentrating these nutritionally valuable lipids into a novel ingredient. In the dairy industry there are several by-products that are rich in phospholipids (PL) such as buttermilk, whey, and whey cream. However, PL are present at low concentrations. To enrich PL in buttermilk powders, regular buttermilk and whey buttermilk (by-product of whey cream after making butter) were microfiltered and then treated with SFE after drying. The total fat, namely nonpolar lipids, in the powders was reduced by 38 to 55%, and phospholipids were concentrated by a factor of 5-fold. Characterization of the PL demonstrated specific molecular fatty amide combinations on the sphingosine (18:1) backbone of sphingomyelin with the greatest proportion being saturated; the most common were 16:0, 20:0, 21:0, 22:0, 23:0, and 24:0. Two unsaturated fatty amide chains, 23:1 and 24:1, were shown to be elevated in a whey cream buttermilk sample compared with the others. However, most unsaturated species were not as abundant.

The applicability of pressurised solvent extraction (PSE) for the quantitative extraction of different of semi-volatiles, including polycyclic aromatic hydrocarbons (PAHs), phenols, polychlorinated biphenyls (PCBs) and total petroleum hydrocarbons have been evaluated. For this study a conventional supercriticalfluid extraction (SFE) system, the Suprex SFE/50 was adapted to function as a pressurised solvent extraction system. Solid samples were weighed into the SFE thimble and extracted using conventional extraction solvents instead of superficial carbon dioxide. Parameters such as extraction temperature and effect of modifiers were investigated. Although limited by the 150 deg. C maximum oven temperature, it was found effective extraction could still be carried out in less than 25 min for all the compounds studied. The technique was applied to different real matrices contaminated with hydrocarbons, PAHs and phenols. Validations of the technique were performed using standard reference materials. Recoveries for these matrices were good (> 75 %) and precision was generally less than a 10 % RSD. Extensive comparison of this technique with sonication and with microwave assisted extraction (MAE) were made, and recoveries were found to be comparable to MAE and superior to sonication. (authors) 15 refs.

Essential oil of Diplotaenia cachrydifolia cultivated in Iran was obtained by supercriticalfluid extraction (SFE) method. The oils were analysed by capillary gas chromatography using flame ionisation and mass spectrometric detections. The compounds were identified according to their retention indices and mass spectra (EI, 70 eV). The effects of different parameters, such as pressure, temperature, modifier volume and extraction times (dynamic and static), on the SFE were inspected by a fractional factorial design (2(5-2)) to identify the significant parameters and their interaction. It showed that static and dynamic times had no effect on the extraction. Finally, a Box-Behnken design was applied to obtain the optimum condition of the significant parameters. The optimal condition was obtained as 30.2 MPa for pressure, 65.6°C for temperature and 258.4 µL for modifier volume. The main components that were extracted with SFE were dillapiole (35.1%), limonene (33.5%) and α-calacorene (25.5%).

Supercriticalfluid assisted atomization introduced by a hydrodynamic cavitation mixer (SAA-HCM) was used to micronize insulin from aqueous solution without use of any organic solvents. Insulin microparticles produced under different operating conditions including solution type, solution concentration and precipitator temperature presented distinct morphologies such as highly folded, partly deflated, corrugated or smooth hollow spherical shape. Solution concentration had a striking influence on particle size, and insulin microparticles produced from acidic solution had mean diameters increasing from 1.4 μm to 2.7 μm when protein concentration increased from 3g/L to 50 g/L. HPLC chromatograms showed no degradation of insulin after SAA-HCM processing and FTIR, CD and fluorescence data further confirmed the structural stability. TGA analysis revealed that insulin microparticles remained moderate moisture content compared with raw material. In vivo study showed that insulin processed by SAA-HCM from acidic solution retained identical bioactivity. SAA-HCM is demonstrated to be a very promising process for insulin inhaled formulation development.

Similar to reversed phase liquid chromatography, basic compounds can be highly challenging to analyze by supercriticalfluid chromatography (SFC), as they tend to exhibit poor peak shape, especially those with high pKa values. In this study, three new stationary phase ligand chemistries available in sub -2 μm particle sizes, namely 2-picolylamine (2-PIC), 1-aminoanthracene (1-AA) and diethylamine (DEA), were tested in SFC conditions for the analysis of basic drugs. Due to the basic properties of these ligands, it is expected that the repulsive forces may improve peak shape of basic substances, similarly to the widely used 2-ethypyridine (2-EP) phase. However, among the 38 tested basic drugs, less of 10% displayed Gaussian peaks (asymmetry between 0.8 and 1.4) using pure CO2/methanol on these phases. The addition of 10mM ammonium formate as mobile phase additive, drastically improved peak shapes and increased this proportion to 67% on 2-PIC. Introducing the additive in the injection solvent rather than in the organic modifier, gave acceptable results for 2-PIC only, with 31% of Gaussian peaks with an average asymmetry of 1.89 for the 38 selected basic drugs. These columns were also compared to hybrid silica (BEH), DIOL and 2-EP stationary phases, commonly employed in SFC. These phases commonly exhibit alternative retention and selectivity. In the end, the two most interesting ligands used as complementary columns were 2-PIC and BEH, as they provided suitable peak shapes for the basic drugs and almost orthogonal selectivities.

New models for describing hydrodynamics and mass transfer performance in supercriticalfluid extraction columns were proposed.Those models were proved by experimental data, which were obtained in supercriticalfluid extraction packed column, spray column and sieve tray column respectively. The inner diameter of those columns are φ25 mm. These experimental systems include supercritical carbon dioxide-isopropanol-water and supercritical carbon dioxide-ethanol-water, in which supercritical carbon dioxide was dispersed phase, and another was continuous phase. The extraction processes were operated with continuous conntercurrent flow. The predicted values are agreed well with ex-perimental data.

Transformer fluid directly affects the working state of the components and the cooling efficiency of transformer. There are three kinds of transformer fluid used for electric locomotive, EMU and suburban rail vehicles: mineral oil, silicone liquid and synthetic ester based insulating oil. In this paper, the three kinds of oil are compared from the fire safety, environmental protection, reliability and low maintenance. It provides a strong basis for the selection of transformer fluid. By compr...

-through labyrinth seals was proposed. A stepped labyrinth seal, which mimics the behavior of the labyrinth seal used in the Sandia National Laboratory (SNL) S-CO2 Brayton cycle, was also tested in the experiment along with simulations performed. The rest of this study demonstrates the difference of valves' behavior under supercriticalfluid and normal fluid conditions. A small-scale valve was tested in the experiment facility using S-CO2. Different percentages of opening valves were tested, and the measured mass flow rate agreed with simulation predictions. Two transients from a real S-CO2 Brayton cycle design provided the data for valve selection. The selected valve was studied using numerical simulation, as experimental data is not available.

This study demonstrates the effect of column selectivity and density of supercritical carbon dioxide (SC-CO2) on the separation of monochloropropanediol (MCPD) esters, known as food toxicants, using SC-CO2 without addition of cosolvent in ultrahigh performance supercriticalfluid chromatography-mass spectrometry (UHPSFC-MS). This study shows that over 20 2-monochloropropanediol (2-MCPD) and 3-monochloropropanediol (3-MCPD) mono- and diesters are separated on a 2-picolylamine column in less than 12 min. The presence and position of a hydroxyl group in the structure, the number of unsaturated bonds, and the acyl chain length play a significant role in the separation of MCPD esters. The flow rate, backpressure, and column oven temperature, which affect the density of the mobile phase, were shown to have a substantial impact on retention, efficiency, and selectivity. The developed method was successfully applied for the determination of MCPD esters in refined oils and showed a close to excellent green analysis score using the Analytical Eco-Scale.

ISEE is an instrument with the potential to perform extractions from regolith found on the surface of asteroids and planets, followed by characterization and quantitation of the extracts using supercriticalfluid extraction (SFE) and chromatography (SFC). SFE is a developed technique proven to extract a wide range of organic compounds. SFC is similar to High Performance Liquid Chromatography (HPLC) but has the advantage of performing chiral separations without needing to derivatize the chiral compounds. CO2 will be the solvent for both stages as it is readily available in the Mars atmosphere. ISEE will capture CO2 from the environment, and use it for SFE and SFC. If successful, this would allow ISEE to perform analysis of organic compounds without using consumables. This paper will present results on a preliminary, proof-of-principle effort to use SFE and SFC to extract and analyze lunar regolith simulant spiked with organic compounds representing a range of organics that ISEE would expect to characterize. An optimization of variables for the extraction of the organics from the spiked regolith was successfully developed, using 138 bar pressure and 40 C temperature. The extraction flow rate was optimized at 2% SLPM with 30% methanol modifier. The extractions were successful with a value of 77.3+/- 0.9% of organics extracted. However, the recovery of organics after the extraction was very low with only 48.5+/-14.2%. Moreover, three columns were selected to analyze multiple samples at a time; two of them are Viridis HSS C18 SB and Torus DIOL, and the third column, specific for chiral separations, has not yet been selected yet.

Importance was studied of making a research on the chemical process technology using the supercriticalfluid. As for its effect on global warming, the amount of CO2 emission was compared during the operation between the conventional process and the process using the supercriticalfluid, the CO2 reduction rate and amount were trially calculated, and a CO2 reduction of a several ten thousand ton scale in carbon conversion was predicted. As to hazardous materials and the reaction of waste retrieval, it was made clear that the process using the supercriticalfluid was valid also for objects for which the chemical process used to be impossible, which indicates a possibility of the widening field of application. Concerning its effect on the energy conservation, energy reduction of several ten thousand tons in heavy oil conversion was predicted by replacing all the existing processes with supercriticalfluids. Relating to the recycling, with the use of supercriticalfluids, the process is possible which produces higher quality and yield and fewer unnecessary products such as char than the conventional process. 197 refs., 102 figs., 71 tabs.

Full Text Available Supercriticalfluid extraction (SFE is a sustainable technique used for the extraction of lipophilic metabolites such as pigments and fatty acids. Arnica plant is considered a potential candidate material with high antioxidant and antimicrobial activities. Therefore, in this study, a locally available Heterotheca inuloides, also known as Mexican arnica, was analyzed for the extraction of high-value compounds. Based on different pressure (P, temperature (T, and co-solvent (CoS, four treatments (T were prepared. A maximum 7.13% yield was recovered from T2 (T = 60 °C, P = 10 MPa, CoS = 8 g/min, followed by 6.69% from T4 (T = 60 °C, P = 30 MPa, CoS = 4 g/min. Some bioactive sesquiterpenoids such as 7-hydroxycadalene, caryophyllene and δ-cadinene were identified in the extracts by GC/MS. The fatty acid profile revealed that the main components were palmitic acid (C16:0, followed by linoleic acid (C18:2ω6c, α-linolenic acid (C18:3ω3 and stearic acid (C18:0 differing in percent yield per treatment. Antibacterial activities were determined by the agar diffusion method, indicating that all the treatments exerted strong antibacterial activity against S. aureus, C. albicans, and E. coli strains. The antioxidant capacity of the extracts was also measured by three in vitro assays, DPPH, TEAC and FRAP, using Trolox as a standard. Results showed high antioxidant capacity enabling pharmaceutical applications of Mexican arnica.

Since high pressures are involved in most plastics forming processes, reliable high-pressure rheological data are required for the simulation of the processes. The effect of pressure is in some ways the reverse of that of temperature; for example increasing temperature decreases the viscosity, while pressure increases it. Supercriticalfluids (SCFs) such as carbon dioxide and nitrogen can act as physical blowing agents in the manufacture of foams and as plasticizers to reduce melt viscosity during processing. The effects of dissolved SCF, pressure, and temperature on the rheological properties of a melt must be known to achieve optimum processing conditions. We used a rotational rheometer and a high-pressure sliding plate rheometer, in which the shear strain, temperature, pressure, and SCF concentration are all uniform. A shear stress transducer senses the stress in the center of the sample to avoid edge effects. It was possible to use shift factors for temperature, pressure and SCF (CO2 or N2) concentration to obtain a master curve. The effect of temperature could be described by the Arrhenius or WLF models, and the effect of pressure was described by the Barus equation. The effect of SCF concentration could be described by the Fujita-Kishimoto equation. The relative effects of pressure and temperature on the viscosity were quantified. To study the effects of short and long chain branching and a phenyl side group, three polymers were used: polyethylene, polypropylene, and polystyrene. We quantified the effects of short- and long-chain branching, pressure, temperature and dissolved SCF on the rheological properties of these three polymers by use of shift factors.

Peach kernels are industrial residues from the peach processing, contain oil with important therapeutic properties and attractive nutritional aspects because of the high concentration of oleic and linoleic acids. The extraction method used to obtain natural compounds from raw matter is critical for product quality definition. Thus, the aim of this work was to compare peach almond extraction yields obtained by different procedures: soxhlet extractions (Sox) with different solvents; hydrodistillation (HD); ethanolic maceration (Mac) followed by fractionation with various solvents, and supercriticalfluid extraction (SFE) at 30, 40 and 50 degrees C and at 100, 200 and 300bar, performed with pure CO(2) and with a co-solvent. The extracts were evaluated with respect to fatty acid composition (FAC), fractionated chemical profile (FCP) and total phenolic content (TPC). The Sox total yields were generally higher than those obtained by SFE. The crossover pressure for SFE was between 260 and 280bar. The FAC results show oleic and linoleic acids as main components, especially for Sox and SFE extracts. The FCP for samples obtained by Sox and Mac indicated the presence of benzaldehyde and benzyl alcohol, components responsible for almond flavor and with important industrial uses, whereas the SFE extracts present a high content of a possible flavonoid. The higher TPC values were obtained by Sox and Mac with ethanol. In general, the maximum pressure in SFE produced the highest yield, TPC and oleic acid content. The use of ethanol at 5% as co-solvent in SFE did not result in a significant effect on any evaluated parameter. The production of peach almond oil through all techniques is substantially adequate and SFE presented advantages, with respect to the quality of the extracts due to the high oleic acid content, as presented by some Sox samples. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Supercriticalfluid extraction (SFE) is a sustainable technique used for the extraction of lipophilic metabolites such as pigments and fatty acids. Arnica plant is considered a potential candidate material with high antioxidant and antimicrobial activities. Therefore, in this study, a locally available Heterotheca inuloides, also known as Mexican arnica, was analyzed for the extraction of high-value compounds. Based on different pressure (P), temperature (T), and co-solvent (CoS), four treatments (T) were prepared. A maximum 7.13% yield was recovered from T2 (T = 60 °C, P = 10 MPa, CoS = 8 g/min), followed by 6.69% from T4 (T = 60 °C, P = 30 MPa, CoS = 4 g/min). Some bioactive sesquiterpenoids such as 7-hydroxycadalene, caryophyllene and δ-cadinene were identified in the extracts by GC/MS. The fatty acid profile revealed that the main components were palmitic acid (C16:0), followed by linoleic acid (C18:2ω6c), α-linolenic acid (C18:3ω3) and stearic acid (C18:0) differing in percent yield per treatment. Antibacterial activities were determined by the agar diffusion method, indicating that all the treatments exerted strong antibacterial activity against S. aureus, C. albicans, and E. coli strains. The antioxidant capacity of the extracts was also measured by three in vitro assays, DPPH, TEAC and FRAP, using Trolox as a standard. Results showed high antioxidant capacity enabling pharmaceutical applications of Mexican arnica.

A new method, which correlates rate constants of chemical reactions and density or pressure in supercriticalfluids, was developed. Based on the transition state theory and thermodynamic principles, the rate constant can be reasonably correlated with the density of the supercriticalfluid, and a correlation equation was obtained.Coupled with the equation of state (EOS) of a supercritical solvent, the effect of pressure on reaction rate constant could be represented. Two typical systems were used to test this method. The result indicates that this method is suitable for dilute supercriticalfluid solutions.

Microalgae contain valuable biologically active lipophilic substances such as omega-3 fatty acids and carotenoids. In contrast to the recovery of vegetable oils from seeds, where the extraction with supercritical CO2 is used as a mild and selective method, economically viable application of this method on similarly soluble oils from microalgae requires, in most cases, much higher pressure. This paper presents and verifies hypothesis that this difference is caused by high adsorption capacity o...

Supercriticalfluid chromatography was used to resolve and determine ginkgolic acids (GAs) and terpene lactones concurrently in ginkgo plant materials and commercial dietary supplements. Analysis of GAs (C13:0, C15:0, C15:1, and C17:1) was carried out by ESI (-) mass detection. The ESI (-) spectra of GAs simply displayed only the [M-H](-) pseudo-molecular ions, and selected ion monitoring (SIM) for those ions was used for the quantification. Analysis of terpene lactones (ginkgolides A, B, C, J and bilobalide) was complicated by in-source collision-induced dissociation (IS-CID) in the ESI source. Thus, MS analysis could be influenced by the fragmentation pattern produced by the IS-CID. However, it was established that the fragmentation pattern, measured by ion survival yield (ISY), was independent of analyte concentration or matrix at a fixed cone voltage in the ESI source. Therefore, MS with SIM mode was applicable for the analysis of these analytes. The reported method provided consistent and sensitive analysis for the analytes of interest. The LOQs and LODs were determined to be below 100 and 40 ng/mL for GAs and 1 μg/mL and 400 ng/mL for terpene lactones, respectively. Intra- and inter-day precisions were found to be satisfactory with RSDs being below 5.2 %. Analyte recoveries ranged from 87 to 109 %. The developed method was successfully applied to the analysis of 11 ginkgo plant samples and 8 dietary supplements with an analysis time of less than 12 min.

Full Text Available Do to the fluctuations associated with the critical region of fluids. The behavior of thermodynamic properties these can not be predicted by mean field theories. To do so, a global equation of state based on the crossover model has been used. This equation of state is formulated on the basis of comparison of selected measurements of pressure-density-temperature data, isochoric and isobaric heat capacity of fluids.The model can be applied in a wide range of temperatures and densities around the critical point for ethane and methane. It is found that the developed model represents most of the reliable experimental data accurately.

This survey consists of 430 references, including 269 Russian publications and 161 Western publications devoted to the problems of heat transfer and hydraulic resistance of a fluid at near-critical and supercritical pressures. The objective of the literature survey is to compile and summarize findings in the area of heat transfer and hydraulic resistance at supercritical pressures for various fluids for the last fifty years published in the open Russian and Western literature. The analysis of the publications showed that the majority of the papers were devoted to the heat transfer of fluids at near-critical and supercritical pressures flowing inside a circular tube. Three major working fluids are involved: water, carbon dioxide, and helium. The main objective of these studies was the development and design of supercritical steam generators for power stations (utilizing water as a working fluid) in the 1950s, 1960s, and 1970s. Carbon dioxide was usually used as the modeling fluid due to lower values of the critical parameters. Helium, and sometimes carbon dioxide, were considered as possible working fluids in some special designs of nuclear reactors. (author)

Global climate change is viewed by many as an anthropogenic phenomenon that could be mitigated through a combination of conservation efforts, alternative energy sources, and the development of technologies capable of reducing carbon dioxide (CO2) emissions. Continued increases of atmospheric CO2 concentrations are projected over the next decade, due to developing nations and growing populations. One economically favorable option for managing CO2 involves subsurface storage in deep basalt formations. The silicate minerals and glassy mesostasis basalt components act as metal cation sources, reacting with the CO2 to form carbonate minerals. Most prior work on mineral reactivity in geologic carbon sequestration settings involves only aqueous dominated reactions. However, in most sequestration scenarios, injected CO2 will reside as a buoyant fluid in contact with the sealing formation (caprock) and slowly become water bearing. Comparatively little laboratory research has been conducted on reactions occurring between minerals in the host rock and the wet scCO2. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably wet supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) in order to gain insight into reaction processes. Mineral transformation reactions were followed by two novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the scCO2 resulted in increased carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared (IR) spectroscopy and indirectly with 18O isotopic labeling techniques (Raman spectroscopy). The thin water films were determined to be critical for facilitating carbonation processes in wet scCO2. Even in extreme low water conditions, the IR technique detected the formation of

Part of the Hewlett Packard Components Group`s Product Stewardship program is the ongoing effort to investigate ways to eliminate or reduce as much as possible the use of chemical substances from manufacturing processes. Currently used techniques to remove hard-baked photoresists from semiconductor wafers require the use of inorganic chemicals or organic strippers and associated organic solvents. Environmental, health and safety, as well as cost considerations prompted the search for alternative, more environmentally-benign, and cost-effective solutions. Two promising, emerging technologies were selected for evaluation: the chilled DI water/ozone technique and supercriticalfluids based on carbon dioxide (CO{sub 2}). Evaluating chilled DI water/ozone shows this process to be effective for positive photoresist removal, but may not be compatible with all metallization systems. Testing of a closed-loop CO{sub 2}-based supercritical CO{sub 2} Resist Remover, or SCORR, at Los Alamos, on behalf of Hewlett-packard, shows that this treatment process is effective in removing photoresists, and is fully compatible with commonly used metallization systems. In this paper, the authors present details on the testing programs conducted with both the chilled DI H{sub 2}O/ozone and SCORR treatment processes.

Full Text Available Abstract The Supercritical Antisolvent (SAS technique allows for the precipitation of drugs and biopolymers in nanometer size in a wide range of industrial applications, while guaranteeing the physical and chemical integrity of such materials. However, a suitable combination of operating parameters is needed for each type of solute. The knowledge of fluid dynamics behavior plays a key role in the search for such parameter combinations. This work presents a numerical study concerning the impact of operating temperature and pressure upon the physical properties and mixture dynamics within the SAS process, because in supercritical conditions the radius of the droplets formed exhibits great sensitivity to these variables. For the conditions analyzed, to account for the heat of mixture in the energy balance, subtle variations in the temperature fields were observed, with almost negligible pressure drop. From analyses of the intensity of segregation, there is an enhancement of the mixture on the molecular scale when the system is operated at higher pressure. This corroborates experimental observations from the literature, related to smaller diameters of particles under higher pressures. Hence, the model resulted in a versatile tool for selecting conditions that may promote a better control over the performance of the SAS process.

Supercritical carbon dioxide fluid extraction (SFE) was studied as a rapid method for extraction of volatile and semivolatile compounds of Chinese commercial cigarettes. The method was compared with simultaneous distillation and extraction (SDE). Temperature and pressure for the SFE were optimized. The extracts obtained by the two methods showed different characters in composition and represented differently the flavor characteristics of tobacco; compared to SDE, SFE can extract compounds within a shorter time and avoid the thermal degradation and solvent contamination of samples. The extracts by the two extraction methods are complementary for investigating the flavor characteristic of tobacco products.

In recent five years, geothermal energy became one of the most prosperous renewable energy in the world, but produces only 0.5% of the global electricity. Why this great potential of green energy cannot replace the fuel and nuclear energy? The necessity of complicated exploration procedures and precious experts in geothermal field is similar to that of the oil and gas industry. The Yilan Plain (NE Taiwan) is one of the hot area for geothermal development and research in the second phase of National Energy Program (NEP-II). The geological and geophysical studies of the area indicate that the Yilan Plain is an extension of the Okinawa Trough back arc rifting which provide the geothermal resource. Based on the new constrains from properties of supercriticalfluids and dissipative structure theory, the geophysical evidence give confident clues on how the geothermal system evolved at depth. The geothermal conceptual model in NEP-II indicates that the volcanic intrusion under the complicate fault system is possibly beneath the Yilan Plain. However, the bottom temperature of first deep drilling and geochemical evidence in NEP-II imply no volcanic intrusion. In contrast, our results show that seismic activities in geothermal field observed self-organization, and are consistent with the brittle-ductile / brittle-plastic transition, which indicates that supercriticalfluids triggered earthquake swarms. The geothermal gradient and geochemical anomalies in Yilan Plain indicate an open system far from equilibrium. Mantle and crust exchange energy and materials through supercriticalfluids to generate a dissipative structure in geothermal fields and promote water-rock interactions and fractures. Our initial studies have suggested a dissipative structure of geothermal system that could be identified by geochemical and geophysical data. The key factor is the tectonic setting that triggered supercriticalfluids upwelling from deep (possibly from the mantle or the upper crust). Our

Impurity profiling of organic products synthesized as possible drug candidates represents a major analytical challenge. Complementary analytical methods are required to ensure that all impurities are detected. Both high-performance liquid chromatography (HPLC) and supercriticalfluid chromatography (SFC) can be used for this purpose. In this study, we compared ultra-high performance HPLC (UHPLC) and ultra-high performance SFC (UHPSFC) using a large dataset of 140 pharmaceutical compounds. Four previously optimized methods (two on each technique) were selected to ensure fast high-resolution separations. The four methods were evaluated based on response rate, peak capacity, peak shape and capability to detect impurities (UV). The orthogonality between all methods was also assessed. The best UHPLC method and UHPSFC methods provided comparable quality for the 140 compounds included in this study. Moreover, they were found to be highly orthogonal. At last, the potential of the combined use of UHPLC and UHPSFC for impurity profiling is illustrated with practical examples.

Full Text Available Transformer fluid directly affects the working state of the components and the cooling efficiency of transformer. There are three kinds of transformer fluid used for electric locomotive, EMU and suburban rail vehicles: mineral oil, silicone liquid and synthetic ester based insulating oil. In this paper, the three kinds of oil are compared from the fire safety, environmental protection, reliability and low maintenance. It provides a strong basis for the selection of transformer fluid. By comprehensive analysis, synthetic ester based insulating oil can completely replace mineral oil and silicone liquid. With rail transport safety and environmental protection standards improving, synthetic ester based insulating oil will be the best choice for transformer.

The objective of this project is to use supercriticalfluids to separate and fractionate algal-based bio-oils into stable products that can be subsequently upgraded to produce drop-in renewable fuels. To accomplish this objective, algae was grown and thermochemically converted to bio-oils using hydrothermal liquefaction (HTL), pyrolysis, and catalytic pyrolysis. The bio-oils were separated into an extract and a raffinate using near-critical propane or carbon dioxide. The fractions were then subjected to thermal aging studies to determine if the extraction process had stabilized the products. It was found that the propane extract fraction was twice as stable as the parent catalytic pyrolysis bio-oils as measured by the change in viscosity after two weeks of accelerated aging at 80°C. Further, in-situ NMR aging studies found that the propane extract was chemically more stable than the parent bio-oil. Thus the milestone of stabilizing the product was met. A preliminary design of the extraction plant was prepared. The design was based on a depot scale plant processing 20,000,000 gallons per year of bio-oil. It was estimated that the capital costs for such a plant would be $8,700,000 with an operating cost of $3,500,000 per year. On a per gallon of product cost and a 10% annual rate of return, capital costs would represent $0.06 per gallon and operating costs would amount to $0.20 per gallon. Further, it was found that the energy required to run the process represented 6.2% of the energy available in the bio-oil, meeting the milestone of less than 20%. Life cycle analysis and greenhouse gas (GHG) emission analysis found that the energy for running the critical fluid separation process and the GHG emissions were minor compared to all the inputs to the overall well to pump system. For the well to pump system boundary, energetics in biofuel conversion are typically dominated by energy demands in the growth, dewater, and thermochemical process. Bio-oil stabilization by

This paper rationalizes the green and scalable synthesis of graphenic materials of different aspect ratios using anthracite coal as a single source material under different supercritical environments. Single layer, monodisperse graphene oxide quantum dots (GQDs) are obtained at high yield (55 wt %) from anthracite coal in supercritical water. The obtained GQDs are ∼3 nm in lateral size and display a high fluorescence quantum yield of 28%. They show high cell viability and are readily used for imaging cancer cells. In an analogous experiment, high aspect ratio graphenic materials with ribbon-like morphology (GRs) are synthesized from the same source material in supercritical ethanol at a yield of 6.4 wt %. A thin film of GRs with 68% transparency shows a surface resistance of 9.3 kΩ/sq. This is apparently the demonstration of anthracite coal as a source for electrically conductive graphenic materials.

A supercritical carbon dioxide (scCO2) based oil extraction method was implemented on olive pomace (alperujo), and an oil yield of 25,5 +/- 0,8% (goil/gdry residue) was obtained. By Soxhlet extraction with hexane, an oil extraction yield of 28,9 +/- 0,8 % was obtained, which corresponds to an efficiency of 88,4 +/- 4,8 % for the supercritical method. The scCO2 extraction process was optimized for operating conditions of 50 MPa and 348,15 K, for which an oil loading of 32,60 g oil/kg CO2 was c...

The study of radial and axial temperature profiles always has been an area interest both in liquid chromatography (LC) and supercriticalfluid chromatography (SFC). Whereas in LC always an increase in temperature is observed due to the dominance of viscous heating, in SFC, especially for low modifier content, a decrease in temperature is found due to the much larger decompression cooling. However, for higher modifier content and higher operating pressure, the temperature effects become a trade-off between viscous heating and decompression cooling, since in SFC the latter is a strong function of operating pressure and mobile phase composition. At a temperature of 40°C and for neat CO2, the effect of decompression cooling and viscous heating cancel each other out at a pressure 450bar. This pressure decreases almost linearly with volume fraction of methanol to 150bar at 25vol%. As a result, both cooling and heating effects can be observed when operating at high back pressure, large column pressure drops or high modifier content. For example at a back pressure of 150bar and a column pressure drop of 270bar decompression cooling is observed throughout the column. However at 300bar back pressure and the same pressure drop, the mobile phase heats up in the first part of the column due to viscous heating and then cools in the second part due to decompression cooling. When coupling columns (2.1mm×150mm, 1.8μm fully porous particles) at very high operating pressure (e.g. 750bar for 8vol%), the situation is even more complex. E.g. at a back pressure of 150bar and using 8vol% methanol, viscous heating is only observed in the first column whereas only decompression cooling in the second. Further increasing the inlet pressure up to 1050bar resulted in no excessive temperature differences along the column. This implies that the inlet pressure of SFC instrumentation could be expanded above 600bar without additional band broadening caused by excessive radial temperature

The supercriticalfluid extraction of Pb(DDC)2 and MoO2(acac)2 complexes is performed. The previously formed complexes are used in order to simplify the extraction process. In the extraction cell, 9.0 mg of Pb(DDC)2 or 30.0 mg of MoO2(acac)2 is added. With these two complexes, a study of static and dynamic extraction as a function of pressure (1000-2500 psi), temperature (40-160 degrees C), and presence of modifier (methanol) is performed. Under the best conditions, 5.6 mg of Pb(DDC)2 (2.3 mg of Pb2+) is recovered. The parameters are 2500 psi of pressure, 160 degrees C of temperature, 0.5 mL methanol (placed in a 10-mL extraction cell), 60.0 min of static extraction, and 2.0 min of dynamic extraction. It is necessary to add 3.0 mL of methanol to enhance efficiency on the MoO2(acac)2 complex recovery. Quantitative extractions of MoO2(acac)2 (9.0 mg of MoVI) are obtained when the experiments are carried out under 1000-2500 psi of pressure, 140 degrees C, and times no longer than 10.0 min. Then, the study is carried out forming the in situ complexes. For this purpose, metallic ion and ligand are added. Under these conditions, the Pb2+ recovery decreases from 2.3 to 1.9 mg, and the MoVI recovery decreases from 9.0 to 1.0 mg. When 1.9 mg of Pb2+ and 1.0 mg of MoVI or less is placed in the extraction cell, the recoveries are always 100%. The Pb2+ extracts are directly accomplished using gas chromatography-flame ionization detection (GC-FID), and the MoVI extracts are analyzed using GC-FID and catalytic adsorption voltammetry. The quantitation of pure extracts is carried out by constructing calibration curves with complex solutions and sample solutions using the standard addition method. This method is applied by determination of Pb2+ in sodium alginate extracted from algae and blood, urine, and human milk from patients with diagnosed plumbunemy. MoVI is determined in irrigation water and pasture of animal intake.

For the task on diffusion coefficients of F-T products in supercriticalfluids, we attempted to find a model for the {beta} parameter to predict the molecular diffusion coefficients to a high degree of accuracy so we may be able to predict both the molecular diffusion coefficient and thus the effective diffusivity a priori. The dependency of solvent/solute interactions on the {beta} parameter was analyzed and a correlation developed to predict the functionality. This allowed us to develop an empirical formula to correlate the molecular diffusion coefficient to ratios of mass, size, and density. Thus finally allowing for supercriticalfluid diffusion predictions a priori. Figure 6 shows our predictions of the data available on the self diffusion coefficient of carbon dioxide (Chen, 1983; Takahashi and Iwasaki, 1966) ethylene (Arends et al., 1981; Baker et al., 1984), toluene (Baker et al., 1985) and chlorotrifuoromethane (Harris, 1978). The predictions, with no parameters adjusted from the data, are excellent with an average absolute error of 3.64%.

Supercritical or near-critical fluid processes for generating microparticles have enjoyed considerable attention in the past decade or so, with good success for substances soluble in supercriticalfluids or organic solvents. In this review, we survey their application to the production of protein particles. A recently developed process known as CO2-assisted nebulization with a Bubble Dryer (CAN-BD) has been demonstrated to have broad applicability to small-molecule as well as macromolecule substances (including therapeutic proteins). The principles of CAN-BD are discussed as well as the stabilization, micronization and drying of a wide variety of materials. More detailed case studies are presented for three proteins, two of which are of therapeutic interest: anti-CD4 antibody (rheumatoid arthritis), alpha1-antitrypsin (cystic fibrosis and emphysema), and trypsinogen (a model enzyme). Dry powders were formed in which stability and activity are maintained and which are fine enough to be inhaled and reach the deep lung. Enhancement of apparent activity after CAN-BD processing was also observed in some formulation and processing conditions.

Using the coupled methods presented in this paper, methylmercury can be accurately and rapidly extracted from biological samples by modified supercriticalfluid carbon dioxide and quantitated using liquid chromatography with reductive electrochemical detection. Supercriticalfluid carbon dioxide modified with methanol effectively extracts underivatized methylmercury from certified reference materials Dorm-1 (dogfish muscle) and Dolt-2 (dogfish liver). Calcium chloride and water, with a ratio of 5:2 (by weight), provide the acid environment required for extracting methylmercury from sample matrices. Methylmercury chloride is separated from other organomercury chloride compounds using HPLC. The acidic eluent, containing 0.06 mol L-1 NaCl, insures the presence of methylmercury chloride and facilitates the reduction of mercury on a glassy carbon electrode. If dual glassy carbon electrodes are used, a positive peak is observed at -0.65 to -0.70 V and a negative peak is observed at -0.90V with the organomercury compounds that were tested. The practical detection limit for methylmercury is 5 X 10-8 mol L-1 (1 X 10-12 tool injected) when a 20 ??L injection loop is used.

Supercriticalfluid extraction (SFE) has been demonstrated to be a useful tool in the determination of additives in polymeric materials. This paper describes the determination of some citrates and benzoates in poly(vinyl chloride) blended with 33-34% of plasticizer using off-line SFE followed by gas chromatography. Experimental factors affecting SFE have been studied by gravimetric analysis, followed by analysis of the extracts using a gas chromatograph equipped with a flame ionization detector. The extraction process is governed by the solubility of the plasticizers in the supercriticalfluid or by their diffusion through the polymer matrix, which depend on the pressure and temperature used. Maximum extraction (>99%) is obtained at pressures and temperatures higher than 40 MPa and 80 degrees C, respectively. Due to purge losses, the collection efficiency of plasticizers into a liquid solvent ranges from 85 to 90%. The applicability of the SFE method is demonstrated using real samples and comparing the results with those obtained by conventional Soxhlet extraction.

The solubilities of TBP and DEHPA in supercritical CO{sub 2} were measured at various equilibrium temperatures(i.e., 313.15, 323.15, 333.15K) and pressures(i.e., 10, 15, 20, 25MPa). It is observed that both the solubilities of TBP and DEHPA are increasing wit increasing temperatures and pressures(ant, thus the density). In general TBP showed higher solubility than DEHPA in CO{sub 2}. were carried out for recovering rare earth elements from the aqueous acidic feed waste solutions. We found that the level of Nd extraction with such supercritically mixed solvent tends to decreasing with increasing HNO{sub 3} and tends to uniform with increasing temperature and pressures. Also, extraction of rare earth TPPO, and TOPO in supercritical CO{sub 2}. For example, the SFE of Nd by these supercritical CO{sub 2}-containing organic solvents showed that the case of TBPO was higher than that of any other organic solvent. (author). 46 refs., 36 figs., 12 tabs.

In the first part of this article the position of supercriticalfluid chromatography (SFC) as an intermediate to gas and liquid chromatography had been treated as well as criteria for the choice of column and pressure control device. In this second part the discussion will be on gradient methods applicable for SFC and on some important fields of application. (orig.).

In this case-based laboratory, an instrument sales person attempts to convince an analysis laboratory of the virtues of supercriticalfluid extraction (SFE). The sales person deals directly with the laboratory technicians who will make the decision. Arrangements are made to have SFE instrumentation brought into the laboratory for a comparative…

In this study the phase behavior of mixtures relevant to the selective catalytic oxidation of benzyl alcohol to benzaldehyde by molecular oxygen in supercritical CO2 is investigated. Initially, the solubility of N2 in benzaldehyde as well as the dew points of CO2–benzyl alcohol–O2 and CO2...

One of the main drawbacks for using lignocellulosic biomass is related to its recalcitrance. The pretreatment of lignocellulosic biomass plays an important role for delignification and crystallinity reduction purposes. In this work rice husk (RH) was submitted to supercritical pretreatment at 80°C and 270 bar with the aim to determine the effect on lignin content, crystallinity as well as enzymatic digestibility. The yields obtained were compared with dilute sulfuric acid pretreatment as base case. Additionally a techno-economic and environmental comparison of the both pretreatment technologies was performed. The results show a lignin content reduction up to 90.6% for the sample with 75% moisture content using a water-ethanol mixture. The results for crystallinity and enzymatic digestibility demonstrated that no reductions were reached. Supercritical pretreatment presents the best economical and environmental performance considering the solvents and carbon dioxide recycling.

This paper describes the laser photopolymerization of a liquid mixture of polyfunctional acrylic monomers, photoinitiator and hydroxyapatite (HA). Pure polymeric and composite materials of specific shape and structure were fabricated by laser stereolithography based on images derived from three-dimensional (3D) computer modeling. The polymeric objects then were treated with supercritical carbon dioxide to remove potentially toxic residues (monomers, low molecular weight oligomers, etc.) and to provide interconnective microporosity. Finally, samples were implanted into white rats (diastolic epiphysis of femoral bone) to study living tissue response and processes of osteointegration and osteoinduction. It was shown that incorporation of HA into the composite implant structure encouraged periosteal as well as endosteal osteogenesis and improved their osteointegrative characteristics in particular. Supercritical carbon dioxide treatment significantly enhanced the biocompatibility of the materials, increasing the area of direct contact of the implant surface with regenerated bone tissue.

Full Text Available The economics of an ORC system is strictly linked to thermodynamic properties of the working fluid. A bad choice of working fluid could lead to a less efficient and expensive plant/generation unit. Some selection criteria have been put forward by various authors, incorporating thermodynamic properties, provided in literature but these do not have a general character. In the paper a simple analysis has been carried out which resulted in development of thermodynamic criteria for selection of an appropriate working fluid for subcritical and supercritical cycles. The postulated criteria are expressed in terms of non-dimensional numbers, which are characteristic for different fluids. The efficiency of the cycle is in a close relation to these numbers. The criteria are suitable for initial fluidselection. Such criteria should be used with other ones related to environmental impact, economy, system size, etc. Examples of such criteria have been also presented which may be helpful in rating of heat exchangers, which takes into account both heat transfer and flow resistance of the working fluid.

Supercriticalfluid extraction (SFE) was performed to extract complex mixtures of polycyclic aromatic hydrocarbons (PAHs), nitrated derivatives (nitroPAHs) and heavy n-alkanes from spiked soot particulates that resulted from the incomplete combustion of diesel oils. This polluted material, resulting from combustion in a light diesel engine and collected at high temperature inside the particulate filter placed just after the engine, was particularly resistant to conventional extraction techniques, such as soxhlet extraction, and had an extraction behaviour that differed markedly from certified reference materials (SRM 1650). A factorial experimental design was performed, simultaneously modelling the influence of four SFE experimental factors on the recovery yields, i.e.: the temperature and the pressure of the supercriticalfluid, the nature and the percentage of the organic modifier added to CO(2) (chloroform, tetrahydrofuran, methylene chloride), as a means to reach the optimal extraction yields for all the studied target pollutants. The results of modelling showed that the supercriticalfluid pressure had to be kept at its maximum level (30 MPa) and the temperature had to be kept relatively low (75 degrees C). Under these operating conditions, adding 15% of methylene chloride to the CO(2) permitted quantitative extraction of not only light PAHs and their nitrated derivatives, but also heavy n-alkanes from the spiked soots. However, heavy polyaromatics were not quantitatively extracted from the refractory carbonaceous solid surface. As such, original organic modifiers were tested, including pyridine, which, as a strong electron donor cosolvent (15% into CO(2)), was the most successful. The addition of diethylamine to pyridine, which enhanced the electron donor character of the cosolvent, even increased the extraction yields of the heaviest PAHs, leading to a quantitative extraction of all PAHs (more than 79%) from the diesel particulate matter, with detection

Supercriticalfluid chromatography, where a low-viscosity mobile phase such as carbon dioxide is used, proves to be an excellent technique for fast and efficient separations, especially when sub-2μm particles are used. However, to achieve high velocities when using these small particles, and in order to stay within the flow rate range of current SFC-instruments, narrow columns (e.g. 2.1mm ID) must be used. Unfortunately, state-of-the-art instrumentation is limiting the full separation power of these narrower columns due to significant extra-column band broadening effects. The present work identifies and quantifies the different contributions to extra-column band broadening in SFC such as the influence of the sample solvent, injection volume, extra-column volumes and detector cell volume/design. When matching the sample solvent to the mobile phase in terms of elution strength and polarity (e.g. using hexane/ethanol/isopropanol 85/10/5vol%) and lowering the injection volume to 0.4μL, the plate count can be increased from 7600 to 21,300 for a low-retaining compound (k'=2.3) on a 2.1mm×150mm column (packed with 1.8μm particles). The application of a water/acetonitrile mixture as sample solvent was also investigated. It was found that when the volumetric ratio of water/acetonitrile was optimized, only a slightly lower plate count was measured compared to the hexane-based solvent when minimizing injection and extra-column volume. This confirms earlier results that water/acetonitrile can be used if water-soluble samples are considered or when a less volatile solvent is preferred. Minimizing the ID of the connection capillaries from 250 to 65μm, however, gives no further improvement in obtained efficiency for early-eluting compounds when a standard system configuration with optimized sample solvent was used. When switching to a state-of-the-art detector design with reduced (dispersion) volume (1.7-0.6μL), an increase in plate count is observed (from 11,000 to 14

The present study describes the chemical composition and the antioxidant activity of spent coffee grounds and coffee husks extracts, obtained by supercriticalfluid extraction (SFE) with CO(2) and with CO(2) and co-solvent. In order to evaluate the high pressure method in terms of process yield, extract composition and antioxidant activity, low pressure methods, such as ultrasound (UE) and soxhlet (SOX) with different organic solvents, were also applied to obtain the extracts. The conditions for the SFE were: temperatures of 313.15K, 323.15K and 333.15K and pressures from 100 bar to 300 bar. The SFE kinetics and the mathematical modeling of the overall extraction curves (OEC) were also investigated. The extracts obtained by LPE (low pressure extraction) with ethanol showed the best results for the global extraction yield (X(0)) when compared to SFE results. The best extraction yield was 15±2% for spent coffee grounds with ethanol and 3.1±04% for coffee husks. The antioxidant potential was evaluated by DPPH method, ABTS method and Folin-Ciocalteau method. The best antioxidant activity was showed by coffee husk extracts obtained by LPE. The quantification and the identification of the extracts were accomplished using HPLC analysis. The main compounds identified were caffeine and chlorogenic acid for the supercritical extracts from coffee husks.

Full Text Available Microbial community structure plays a significant role in environmental assessment and animal health management. The development of a superior analytical strategy for the characterization of microbial community structure is an ongoing challenge. In this study, we developed an effective supercriticalfluid extraction (SFE and ultra performance liquid chromatography (UPLC method for the analysis of bacterial respiratory quinones (RQ in environmental and biological samples. RQ profile analysis is one of the most widely used culture-independent tools for characterizing microbial community structure. A UPLC equipped with a photo diode array (PDA detector was successfully applied to the simultaneous determination of ubiquinones (UQ and menaquinones (MK without tedious pretreatment. Supercritical carbon dioxide (scCO2 extraction with the solid-phase cartridge trap proved to be a more effective and rapid method for extracting respiratory quinones, compared to a conventional organic solvent extraction method. This methodology leads to a successful analytical procedure that involves a significant reduction in the complexity and sample preparation time. Application of the optimized methodology to characterize microbial communities based on the RQ profile was demonstrated for a variety of environmental samples (activated sludge, digested sludge, and compost and biological samples (swine and Japanese quail feces.

The design of a new interface to hyphen high efficiency supercriticalfluid chromatography (SFC) and fast RPLC in a comprehensive configuration is described. SFC x RPLC is a viable alternative to normal phase (NP) LC x RPLC and is characterized by high orthogonality. Compared to NPLC x RPLC an additional advantage is the expansion of supercritical carbon dioxide (CO(2)) when exposed to atmospheric pressure leading to fractions consisting of solvents that are miscible with the second dimension RPLC mobile phase. The interface consists of a two-position/ten-port switching valve equipped with two packed octadecyl silica (C(18)) loops for effective trapping and focusing of the analytes after elution from the SFC dimension. The addition of a water make-up flow to the SFC effluent prior to entering the loops is of fundamental importance to efficiently focus the solutes on the C(18) material and to reduce interferences of expanded CO(2) gas on the second dimension separation. The features of the system are illustrated with the analysis of a lemon oil sample.

We demonstrate the use of inverse supercritical carbon dioxide (scCO2) extraction as a novel method of sample preparation for the analysis of complex nanoparticle-containing samples, in our case a model sunscreen agent with titanium dioxide nanoparticles. The sample was prepared for analysis in a simplified process using a lab scale supercriticalfluid extraction system. The residual material was easily dispersed in an aqueous solution and analyzed by Asymmetrical Flow Field-Flow Fractionation (AF4) hyphenated with UV- and Multi-Angle Light Scattering detection. The obtained results allowed an unambiguous determination of the presence of nanoparticles within the sample, with almost no background from the matrix itself, and showed that the size distribution of the nanoparticles is essentially maintained. These results are especially relevant in view of recently introduced regulatory requirements concerning the labeling of nanoparticle-containing products. The novel sample preparation method is potentially applicable to commercial sunscreens or other emulsion-based cosmetic products and has important ecological advantages over currently used sample preparation techniques involving organic solvents.

Microbial community structure plays a significant role in environmental assessment and animal health management. The development of a superior analytical strategy for the characterization of microbial community structure is an ongoing challenge. In this study, we developed an effective supercriticalfluid extraction (SFE) and ultra performance liquid chromatography (UPLC) method for the analysis of bacterial respiratory quinones (RQ) in environmental and biological samples. RQ profile analysis is one of the most widely used culture-independent tools for characterizing microbial community structure. A UPLC equipped with a photo diode array (PDA) detector was successfully applied to the simultaneous determination of ubiquinones (UQ) and menaquinones (MK) without tedious pretreatment. Supercritical carbon dioxide (scCO(2)) extraction with the solid-phase cartridge trap proved to be a more effective and rapid method for extracting respiratory quinones, compared to a conventional organic solvent extraction method. This methodology leads to a successful analytical procedure that involves a significant reduction in the complexity and sample preparation time. Application of the optimized methodology to characterize microbial communities based on the RQ profile was demonstrated for a variety of environmental samples (activated sludge, digested sludge, and compost) and biological samples (swine and Japanese quail feces).

An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercriticalfluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method.

The waste oil used in nuclear fuel processing is contaminated with uranium because of its contact with materials or environments containing uranium. Under current law, waste oil that has been contaminated with uranium is very difficult to dispose of at a radioactive waste disposal site. To dispose of the uranium-contaminated waste oil, the uranium was separated from the contaminated waste oil. Supercritical R-22 is an excellent solvent for extracting clean oil from uranium-contaminated waste oil. The critical temperature of R-22 is 96.15 °C and the critical pressure is 49.9 bar. In this study, a process to remove uranium from the uranium-contaminated waste oil using supercritical R-22 was developed. The waste oil has a small amount of additives containing N, S or P, such as amines, dithiocarbamates and dialkyldithiophosphates. It seems that these organic additives form uranium-combined compounds. For this reason, dissolution of uranium from the uranium-combined compounds using nitric acid was needed. The efficiency of the removal of uranium from the uranium-contaminated waste oil using supercritical R-22 extraction and nitric acid treatment was determined.

The volatiles from Coriandrum sativum L., Satureja montana L., Santolina chamaecyparissus L., and Thymus vulgaris L. were isolated by hydrodistillation (essential oil) and supercriticalfluid extraction (volatile oil). Their effect on seed germination and root and shoot growth of the surviving seedlings of four crops ( Zea mays L., Triticum durum L., Pisum sativum L., and Lactuca sativa L.) and two weeds ( Portulaca oleracea L. and Vicia sativa L.) was investigated and compared with those of two synthetic herbicides, Agrocide and Prowl. The volatile oils of thyme and cotton lavender seemed to be promising alternatives to the synthetic herbicides because they were the least injurious to the crop species. The essential oil of winter savory, on the other hand, affected both crop and weeds and can be appropriate for uncultivated fields.

Determination of free fatty acids (FFAs) in food products is of enormous interest mainly because they are related to the quality and authenticity of the oils. In this study, supercriticalfluid chromatography (SFC), followed by an electrospray ionisation triple-quadrupole mass spectrometry (ESI-MS), is shown to provide a novel method for the separation and detection of FFAs in edible oils without any pretreatment. Eight FFAs were separated on a HSS C18 SB column with gradient elution within 3 min. Effects of different columns, modifiers and column temperature changes were evaluated. The results indicated the feasibility of this method for the high-throughput determination of individual FFAs with satisfactory correlation coefficients (R(2)>0.994) and good reproducibility of RSDoil were successfully distinguished into several categories, showing a potential application for the determination of oil quality or authenticity.

Solvent-free microparticles, loaded with bovine serum albumin as a model protein, were produced using a novel supercritical (SC) fluid-based coating technology. Coating material consists either of trimyristin (Dynasan 114) or of Gelucire 50-02. Microparticles obtained were characterized as regards their morphology, protein content and in vitro release profile. A discontinuous coating made of micro-needles of trimyristin led to an initial burst release of approximately 70% in 30 min. However, a prolonged release of the BSA could be achieved in a phosphate buffer solution at 37 degrees C over a 24 h period from particles coated with Gelucire 50-02. Furthermore, it was shown that BSA does not undergo any degradation after SC CO(2) treatment under the conditions used in the coating process.

Full Text Available In this work, LiCoPO4 nanoparticles were synthesized by supercriticalfluid method using cobalt nitrate hexahydrate (Co(NO32 6H2O and cobalt acetate tetrahydrate (C4H6CoO4 4H2O as starting materials. The effect of starting materials on particle morphology, size, and the crystalline phase were investigated. The as-synthesized samples were systematically characterized by XRD, TEM, STEM, EDS, BET, and TG and charge-discharge measurements. In addition, Rietveld refinement analysis was performed. The electrochemical measurements of LiCoPO4 nanoparticles have shown differences in capacities depending on the starting materials used in the synthesis and the results have been discussed in this paper.

The analysis of several plasticizers, widely used in the production of medical devices, was investigated on porous graphitic carbon (PGC) stationary phase in supercriticalfluid chromatography (SFC) with an evaporative light scattering detector (ELSD). Due to strong interaction of compounds with the PGC support, solvents of strong eluotropic strength were added to the CO2 supercriticalfluid. The effect of alkyl chain (pentane, hexane, heptane) and chlorinated (CH2Cl2, CHCl3, CCl4) solvents was studied on the retention and on the ELSD detection of plasticizers. A co-solvent mixture composed of CHCl3/heptane, eluted under gradient mode, allowed a significant improvement of the ELSD response compared to the use of each solvent individually. Then, a central composite design (CCD) was implemented to optimize both the separation and the detection of plasticizers. The parameters involved were the outlet pressure, the gradient slope, the co-solvent composition and the drift tube temperature of the ELSD. After optimization, baseline separation of plasticizers was achieved in 7min and best signal-to-noise ratios were obtained with outlet pressure and drift tube temperature of ELSD set at 200bar and 31°C, respectively. The co-solvent mixture was also composed of CHCl3/heptane (35/65 v/v) and a gradient from 15 to 60% of co-solvent in 2.2min was employed. The results demonstrated that CCD is a powerful tool for the optimization of SFC/ELSD method and the response surface model analysis can provide statistical understandings of the significant factors required to achieve optimal separation and ELSD sensitivity.

Enantiomeric separation of six triazole fungicides: triadimefon, hexaconazole, tebuconazole, difenoconazole, uniconazole, myclobutanil, was conducted on chiral column Chiralpak IB (a new chiral stationary phase containing cellulose tris(3, 5-dimethylphenylcara bamate) immobilized onto silica gel) using supercriticalfluid chroma tography, and the influence of alcohol modifiers methanol, ethanol and isopropanol in mobile phase (super-critical CO2) on the enantio-separation was studied. All fungicides* except difenoconazole, were obtained baseline separation; and in most cases the retention time was shorter than lOmin. The retention and resolution of the samples were obviously influenced by the concentration and type of the modifier. The separation results were satisfactory because the modifier showed good selectivity for the chiral pesticide to be separated.%采用超临界流体色谱(SFC),在Chiralpak IB(一种新型的纤维素衍生物键合型手性固定相)上对三唑酮、己唑醇、戊唑醇、烯效唑、腈菌唑以及恶醚唑等6种三唑类杀菌剂进行了手性拆分,并分析讨论了甲醇、乙醇和异丙醇三种醇类流动相改性剂对手性农药分离的影响.实验结果表明,除恶醚唑外,其他5种农药手性对映体都获得了基线分离,且大部分的手性分离时间在10 min以内.改性剂的浓度和种类对手性分离的保留时间和分离都有一定影响,不同的改性剂适于拆分不同的农药.

Techniques for generating power are provided. Such techniques involve a thermodynamic system including a housing, a turbine positioned in a turbine cavity of the housing, a compressor positioned in a compressor cavity of the housing, and an alternator positioned in a rotor cavity between the turbine and compressor cavities. The compressor has a high-pressure face facing an inlet of the compressor cavity and a low-pressure face on an opposite side thereof. The alternator has a rotor shaft operatively connected to the turbine and compressor, and is supported in the housing by bearings. Ridges extending from the low-pressure face of the compressor may be provided for balancing thrust across the compressor. Seals may be positioned about the alternator for selectively leaking fluid into the rotor cavity to reduce the temperature therein.

Full Text Available Tissue engineering scaffolds require a controlled pore size and structure to host tissue formation. Supercritical carbon dioxide (scCO2 processing may be used to form foamed scaffolds in which the escape of CO2 from a plasticized polymer melt generates gas bubbles that shape the developing pores. The process of forming these scaffolds involves a simultaneous change in phase in the CO2 and the polymer, resulting in rapid expansion of a surface area and changes in polymer rheological properties. Hence, the process is difficult to control with respect to the desired final pore size and structure. In this paper, we describe a detailed study of the effect of polymer chemical composition, molecular weight and processing parameters on final scaffold characteristics. The study focuses on poly(DL-lactic acid (PDLLA and poly(DL-lactic acid-co-glycolic acid (PLGA as polymer classes with potential application as controlled release scaffolds for growth factor delivery. Processing parameters under investigation were temperature (from 5 to 55oC and pressure (from 60 to 230 bar. A series of amorphous PDLLA and PLGA polymers with various molecular weights (from 13 KD to 96 KD and/or chemical compositions (the mole percentage of glycolic acid in the polymers was 0, 15, 25, 35 and 50 respectively were employed. The resulting scaffolds were characterised by optical microscopy, scanning electron microscopy (SEM, and micro X-ray computed tomography (µCT. This is the first detailed study on using these series polymers for scaffold formation by supercritical technique. This study has demonstrated that the pore size and structure of the supercritical PDLLA and PLGA scaffolds can be tailored by careful control of processing conditions.

The behavior of thermodynamic response functions and the thermodynamic scalar curvature in the supercritical region have been studied for a Lennard-Jones fluid based on a revised modified Benedict-Webb-Rubin equation of state. Response function extrema are sometimes used to estimate the Widom line, which is characterized by the maxima of the correlation lengths. We calculated the Widom line for the Lennard-Jones fluid without using any response function extrema. Since the volume of the correlation length is proportional to the Riemannian thermodynamic scalar curvature, the locus of the Widom line follows the slope of maximum curvature. We show that the slope of the Widom line follows the slope of the isobaric heat capacity maximum only in the close vicinity of the critical point and that, therefore, the use of response function extrema in this context is problematic. Furthermore, we constructed the vapor-liquid coexistence line for the Lennard-Jones fluid using the fact that the correlation length, and therefore the thermodynamic scalar curvature, must be equal in the two coexisting phases. We compared the resulting phase envelope with those from simulation data where multiple histogram reweighting was used and found striking agreement between the two methods.

Background: The ultimate goal of the study is the improvement of predictive methods for safety analyses and design of Generation IV reactor systems such as supercritical water reactors (SCWR) for higher efficiency, improved performance and operation, design simplification, enhanced safety and reduced waste and cost. The objective of this Korean / US / laboratory / university collaboration of coupled fundamental computational and experimental studies is to develop the supporting knowledge needed for improved predictive techniques for use in the technology development of Generation IV reactor concepts and their passive safety systems. The present study emphasizes SCWR concepts in the Generation IV program.

Supercriticalfluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercriticalfluids. The special properties of supercriticalfluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity) have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercriticalfluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a “molecular memory”, i.e., the capacity to “remember” a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercriticalfluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor), on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life. PMID:25370376

Full Text Available Supercriticalfluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercriticalfluids. The special properties of supercriticalfluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercriticalfluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a “molecular memory”, i.e., the capacity to “remember” a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercriticalfluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor, on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life.

Supercriticalfluids have different properties compared to regular fluids and could play a role as life-sustaining solvents on other worlds. Even on Earth, some bacterial species have been shown to be tolerant to supercriticalfluids. The special properties of supercriticalfluids, which include various types of selectivities (e.g., stereo-, regio-, and chemo-selectivity) have recently been recognized in biotechnology and used to catalyze reactions that do not occur in water. One suitable example is enzymes when they are exposed to supercriticalfluids such as supercritical carbon dioxide: enzymes become even more stable, because they are conformationally rigid in the dehydrated state. Furthermore, enzymes in anhydrous organic solvents exhibit a "molecular memory", i.e., the capacity to "remember" a conformational or pH state from being exposed to a previous solvent. Planetary environments with supercriticalfluids, particularly supercritical carbon dioxide, exist, even on Earth (below the ocean floor), on Venus, and likely on Super-Earth type exoplanets. These planetary environments may present a possible habitat for exotic life.

Selective hydrogenation of citral was investigated over Au-based bimetallic catalysts in the environmentally benign supercritical carbon dioxide (scCO2) medium.The catalytic performances were different in citral hydrogenation when Pd or Ru was mixed (physically and chemically) with Au.Compared with the corresponding monometallic catalyst,the total conversion and the selectivity to citronellal (CAL) were significantly enhanced over TiO2 supported Pd and Au bimetallic catalysts (physically and chemically mixed);however,the conversion and selectivity did not change when Ru was physically mixed with Au catalyst compared to the monometallic Ru/TiO2,and the chemically mixed Ru-Au/TiO2 catalyst did not show any activity.The effect of CO2 pressure on the conversion of citral and product selectivity was significantly different over the Au/TiO2,Pd-Au/TiO2,and Pd/TiO2 catalysts.It was assumed to be ascribed to the difference in the interactions between Au,Pd nanoparticles and CO2 under different CO2 pressures.

One approach to the prevention of pollution and the reduction of worker exposure from conventional solvents is the use of less hazardous substitutes. One of the more novel substitutes is carbon dioxide. Although carbon dioxide is a gas at ordinary conditions, it can be liquified by application of pressure. In its supercritical state, it exhibits good solvent properties. Separation of the carbon dioxide from the extracted materials can be accomplished by pressure reduction, adsorption onto activated carbon, or with a membrane process, e.g., decaffeination of coffee. This paper presents a brief overview of the university and federal laboratory collaborative efforts focusing on processes using supercritical carbon dioxide as a substitute for hazardous solvents. The SCCO2 technology applications under this program include extraction of natural pharmaceutical materials, phase-transfer catalysis, solvent replacement in chemical synthesis, temperature-solubility relationships, and separation of organic materials from soils and slurries. A paper on the extraction of heavy metals with SCCO2 was presented by Ataai et.al. at the 87th National Meeting, A&WMA. This work is also supported by the EPA.

To research the optimal extraction process of supercritical CO2 extraction and analyze the component of the oil extracted from leaves of Taxus chinensis var. mairei. Using the yield of leaves oil from Taxus chinensis var. mairei as the index, investigated the effect of the extraction pressure, extraction temperature and extraction time on the extracting-rate of leaves oil. The chemical composition of the extracted leaves oil was analyzed by derivatized GC-MS. The optimal parameters of the supercritical CO2 extraction of the oil extracted from leaves of Taxus chinensis var. mairei were determined: CO2 compressor pump frequency was 10 Hz, the extraction pressure was 25 MPa and the temperature of extraction was 45 degrees C, the extraction time was 120 min, the isolator I pressure was 8.0 MPa and the temperature of extraction was 40 degrees C, the isolator II pressure was 5.0 MPa and the temperature of extraction was 35 degrees C. The extracted leaves oil was derivatized with boron trifluoride-methanol complex. Thirty-three kinds of fatty acids were identified by GC-MS. The yield of leaves oils are different from Taxus chinensis var. mairei from 3 habitats. The yield of leaves oil from Donggang, Wuxi city is the highest, about 2.61%. The kinds of fatty acids with high amounts in leaves oil from Taxus chinensis var. mairei is identical in general, the kinds of fatty acids with low amounts in leaves oil from Taxus chinensis var. mairei have differences.

The current study was carried out to develop an environmental benign process for direct recovery of palladium (Pd) and silver (Ag) from waste printed circuit boards (PCBs) powder. The process ingeniously combined supercritical water oxidation (SCWO) and supercritical carbon dioxide (Sc-CO2) extraction techniques. SCWO treatment could effectively enrich Pd and Ag by degrading non-metallic component, and a precious metal concentrate (PMC) could be obtained, in which the enrichment factors of Pd and Ag reached 5.3 and 4.8, respectively. In the second stage, more than 93.7% Pd and 96.4% Ag could be extracted from PMC by Sc-CO2 modified with acetone and KI-I2 under optimum conditions. Mechanism study indicated that Pd and Ag extraction by Sc-CO2 was a complicated physiochemical process, involving oxidation, complexation, anion exchange, mass transfer and migration approaches. Accordingly, this study established a benign and effective process for selective recovery of dispersal precious metals from waste materials.

Epoxy carotenoids, which are products of carotenoid oxidation, are potential oxidative stress markers. However, it is difficult to profile epoxy carotenoids owing to their small amount and difficulty in their separation from hydroxy carotenoids. In this study, a high-performance analytical system based on supercriticalfluid chromatography (SFC) coupled with tandem mass spectrometry (MS/MS) was developed for the simultaneous analysis of carotenoids and epoxy carotenoids. SFC is an effective separation technique for hydrophobic compounds, by which major carotenoids in human serum and their epoxidation products can be analyzed within 20 min. The use of MS/MS increased the sensitivity; the detection limit for each carotenoid was of the sub-fmol order. When the constructed method was applied to biological samples such as human serum and low-density lipoprotein (LDL), the precise detection of the target carotenoids was disturbed by several isomers. However, highly selective detection of epoxy carotenoids was performed by targeting product ions that were generated with a structure-specific neutral loss of 80Da. Furthermore, the sample volume needed for the analysis was only 0.1ml for the serum, indicating the efficiency of this system in performing small-scale analyses. Using the analytical system developed in this study, highly sensitive and selective analysis of epoxy carotenoids could be performed in a short time. These features show the usefulness of this system in application to screening analysis of carotenoid profiles that are easily modified by oxidative stress.

Full Text Available Argan oil has been extracted using supercritical CO2. The influence of the variables pressure (100, 200, 300, and 400 bar and temperature (35, 45, 55°C was investigated. The best extraction yields were achieved at a temperature of 45°C and a pressure of 400 bar. The argan oil extracts were characterized in terms of acid, peroxide and iodine values, total tocopherol, carotene, and fatty acids content. Significant compositional differences were not observed between the oil samples obtained using different pressures and temperatures. The antioxidant capacity of the argan oil samples was high in comparison to those of walnut, almond, hazelnut, and peanut oils and comparable to that of pistachio oil. The physicochemical parameters of the extracted oils obtained by SFE, Soxhlet, and traditional methods are comparable. The technique used for oil processing does not therefore markedly alter the quality of argan oil.

Full Text Available In this study, Flaxseed oil was extracted by Supercritical Carbondioxide Extraction, and extractionkinetics was modelled using diffusion controlled method.The effect of process parameters, such as pressure (20, 35, 55 MPa, temperature (323 and 343 K, and CO2 flow rate (1 and 3 L CO2 /min on the extraction yield and effective diffusivity (De was investigated. The effective diffusion coefficient varied between 2.4 x10-12 and 10.8 x10-12 m2s-1 for the entire range of experiments and increased with the pressure and flow rate. The model fitted well theexperimental data (ADD varied between 2.35 and 7.48%.

A rapid, convenient and environmentally benign method has been developed for the fabrication of metal nanoparticle/multiwall carbon nanotube (MWCNT) composites. Nanoparticles of palladium, rhodium and ruthenium are deposited onto functionalized MWCNTs through a simple hydrogen reduction of metal-?-diketone precursors in supercritical carbon dioxide, and are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analyses. These highly dispersed nanoparticles, with a narrow range of size distribution and good adhesion on MWCNT surfaces, are expected to exhibit promising catalytic properties for a variety of chemical reactions. Preliminary experiments demonstrate that Pd nanoparticles supported on MWCNTs are effective catalysts for hydrogenation of olefins in carbon dioxide. The Pd nanoparticle?MWCNT composite also shows a high electrocatalytic activity in oxygen reduction for potential fuel cell application.

A method of reactivating a catalyst, such as a solid catalyst or a liquid catalyst. The method comprises providing a catalyst that is at least partially deactivated by fouling agents. The catalyst is contacted with a fluid reactivating agent that is at or above a critical point of the fluid reactivating agent and is of sufficient density to dissolve impurities. The fluid reactivating agent reacts with at least one fouling agent, releasing the at least one fouling agent from the catalyst. The at least one fouling agent becomes dissolved in the fluid reactivating agent and is subsequently separated or removed from the fluid reactivating agent so that the fluid reactivating agent may be reused. A system for reactivating a catalyst is also disclosed.

The aim of this study was to enhance the apparent solubility and dissolution properties of flurbiprofen through inclusion complexation with cyclodextrins. Especially, the efficacy of supercriticalfluid technology as a preparative technique for the preparation of flurbiprofen-methyl-β-cyclodextrin inclusion complexes was evaluated. The complexes were prepared by supercritical carbon dioxide processing and were evaluated by solubility, differential scanning calorimetry, X-ray powder diffraction, scanning electron microscopy, practical yield, drug content estimation and in vitro dissolution studies. Computational molecular docking studies were conducted to study the possibility of molecular arrangement of inclusion complexes between flurbiprofen and methyl-β-cyclodextrin. The studies support the formation of stable molecular inclusion complexes between the drug and cyclodextrin in a 1:1 stoichiometry. In vitro dissolution studies showed that the dissolution properties of flurbiprofen were significantly enhanced by the binary mixtures prepared by supercritical carbon dioxide processing. The amount of flurbiprofen dissolved into solution alone was very low with 1.11±0.09% dissolving at the end of 60min, while the binary mixtures processed by supercritical carbon dioxide at 45°C and 200bar released 99.39±2.34% of the drug at the end of 30min. All the binary mixtures processed by supercritical carbon dioxide at 45°C exhibited a drug release of more than 80% within the first 10min irrespective of the pressure employed. The study demonstrated the single step, organic solvent-free supercritical carbon dioxide process as a promising approach for the preparation of inclusion complexes between flurbiprofen and methyl-β-cyclodextrin in solid-state.

Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. Their total amount in the commercial lubricant varies from a few percents to 20-25%. As they belong to various chemical classes and are added to a very complex medium, the base stock, their detailed chromatographic analysis is very difficult and time consuming as it should involve sample treatment and preparative scale separations in order to simplify the sample. The aim of this work is to determine the feasibility of the separation of low molecular weight lubricant additives using various packed columns with pure CO(2) as a mobile phase to enable implementation of flame ionisation detection as universal detector. This is part of a hypernated system including more sophisticated specific detectors, such as AED, FTIR or MS to obtain detailed structural information of compounds. This paper is devoted to the comparison of some stationary phases supposed to provide hydrocarbon group type separation (silica and normal phase) or separations on alkyl-bonded silica in non-aqueous mode of some selected classes of additives in test mixtures or in base stocks. Adsorption chromatography allows partial separation of additives from the base stocks while the direct elution of test additives can only be obtained on reversed phase supports having a very efficient silanol group protection so the interaction of the more polar compounds is much reduced. A two-dimensional scheme of analysis is also described. It combines adsorption chromatography to separate most of the polar additives from the base stock and alkyl-bonded silica for more detailed separation of the additives. However, overlapping between groups of compounds and the lack of resolution between some additives and the base stock should be addressed by the implementing of selective detectors.

Objective: To extract three kinds of tanshinones from the root of Salvia miltiorrhiza Bunge by CO2-supercriticalfluid extraction technology with different entrainers at different flow rates, and to investigate the effects of different entrainers. Methods:Three kinds of tanshinones were extracted at the optimal operation condition, and the massconcentration of three kinds of tanshinones in the extracts was determined by HPLC. Results: Among the three entrainers, the extracting effects of ethanol is the best, for the stronger polarity, followed by ethanol and normal octane. Conclusion: To increase the extracting rate of three kinds of tanshinones by CO2-supercriticalfluid extraction technics, it is essential to use polar solvent as entrainer.

Fe2O3/TiO2 nanocomposite photocatalysts were synthesized by supercriticalfluid combination technique, consisting of sol-gel method and supercriticalfluid drying. The photocatalytic activity of the samples was evaluated by the degradation of acrylic acid. The results indicated that the Fe2O3/TiO2 nanocomposite catalysts prepared by this novel technique showed significant improvement in catalytic activity compared with pure TiO2 or Fe2O3/TiO2 catalysts prepared by traditional drying. Both infrared and ultraviolet spectrum of Fe2O3/TiO2 nanocomposite photocatalysts shift a little to lower wavelength indicating that the absorption threshold of Fe doped nanocomposite photocatalysts shift into the visible light region. This phenomenon was also attested by the photocatalytic degradation test under visible light.

Six supercriticalfluid extraction (SFE) methods were tested, by varying the following operational parameters: CO2 pressure, time and temperature of extraction, type and proportion of static modifier, and Hydromatrix®/sample rate into cell. Firstly, insecticide carbamates were extracted from spiked potatoes samples (fortification level of 0,5 mg.Kg-1) by using SPE procedures, and then final extracts were analyzed HPLC/fluorescence. Good performance was observed with SFE methods that operated ...

Full Text Available The first two papers in this series described the basic theory involved in supercriticalfluid chromatography (SFC, how the technique evolved from gas and liquid chromatography and how the instrumentation was developed. Over the last two years, a commercial, dedicated packed-column SFC/MS instrument appeared on the market. The SFC continues to grow in use, with fundamental developments, coupled with a steady rise in the number of industrial users and applications.

Full Text Available Eucalyptus bark contains significant amounts of triterpenoids with demonstrated bioactivity, namely triterpenic acids and their acetyl derivatives (ursolic, betulinic, oleanolic, betulonic, 3-acetylursolic, and 3-acetyloleanolic acids. In this work, the supercriticalfluid extraction (SFE of Eucalyptusglobulus deciduous bark was carried out with pure and modified carbon dioxide to recover this fraction, and the results were compared with those obtained by Soxhlet extraction with dichloromethane. The effects of pressure (100–200 bar, co-solvent (ethanol content (0, 5 and 8% wt, and multistep operation were studied in order to evaluate the applicability of SFE for their selective and efficient production. The individual extraction curves of the main families of compounds were measured, and the extracts analyzed by GC-MS. Results pointed out the influence of pressure and the important role played by the co-solvent. Ethanol can be used with advantage, since its effect is more important than increasing pressure byseveral tens of bar. At 160 bar and 40 °C, the introduction of 8% (wt of ethanol greatly improves the yield of triterpenoids more than threefold.

The use of phase appropriate technologies is critical for efficiently moving drug candidates forward in the early stages of drug discovery and development. Phase appropriate purification technology develops the analytical method and subsequently scales up the method and turns the sample around quickly (Kennedy et al., J Chromatogr A 2004; 1046:55). In this article, separation results and conditions from supercriticalfluid chromatography (SFC), high-performance liquid chromatography (HPLC), and steady-state recycling (SSR) for the resolutions of three pharmaceutical intermediates in the early stage of the drug development are discussed. The first study used SFC and SSR to separate an impurity for a Good Manufacturing Practice (GMP) campaign. The analytical method development and scale-up conditions are discussed. Productivity, solvent usage, and sample solubility under SFC and SSR conditions are also compared. The second study compared SFC to batch HPLC in separating a diastereomer. Due to higher separation efficiency, SFC was able to resolute multiple peaks. The third study involved the addition of dichloromethane as a co-solvent in SFC purification--improving sample selectivity and solubility. From the separation results of these purifications, SFC and SSR are clearly phase appropriate technologies in the early drug development stage.

An analytical method using supercritical-fluid chromatography coupled with diode-array detection for the determination of seven emerging contaminants-two pharmaceuticals (carbamazepine and glyburide), three endocrine disruptors (17α-ethinyl estradiol, bisphenol A, and 17β-estradiol), one bactericide (triclosan), and one pesticide (diuron)-was developed and validated. These contaminants were chosen because of their frequency of use and their toxic effects on both humans and the environment. The optimized chromatographic separation on a Viridis BEH 2-EP column achieved baseline resolution for all compounds in less than 10 min. This separation was applied to environmental water samples after sample preparation. The optimized sample treatment involved a preconcentration step by means of solid-phase extraction using C18-OH cartridges. The proposed method was validated, finding recoveries higher than 94 % and limits of detection and limits of quantification in the range of 0.10-1.59 μg L(-1) and 0.31-4.83 μg L(-1), respectively. Method validation established the proposed method to be selective, linear, accurate, and precise. Finally, the method was successfully applied to environmental water samples.

The enantiomeric separations of three neonicotinoid insecticides (identified as compounds 1, 2, and 3) were performed on three polysaccharide-type chiral columns, that is, Chiralcel OD-H, Chiralpak AD-H, and Chiralpak IB, by high-performance liquid chromatography (HPLC) and supercriticalfluid chromatography (SFC). Effects of the modifier percentage and column temperature on chiral recognitions of chiral stationary phases were also studied. Both 1 and 2 could be resolved on all three columns selected, with the highest R(s) values obtained on Chiralpak AD-H and Chiralcel OD-H, respectively. However, satisfactory separation of the four stereoisomers of 3 was only achieved on Chiralcel OD-H. Considering the effects of ethanol on the values of k, α, and R(s), we concluded that hydrogen bonding, π-π, and/or dipole-dipole interactions might be all responsible for the chiral separation. In comparison to HPLC, a shorter run time was achieved for 1 and 2 by SFC. However, 3 could not be stereoselectively resolved using SFC. On the basis of the calculated thermodynamic parameters, we found that the separation processes of enantiomers of 1 and 2 were entropy controlled and enthalpy controlled, respectively.

A method for enantiomeric separation of the three β-blocking agents atenolol, metoprolol, propranolol and the zwitterionic metoprolol acid, a major metabolite of both metoprolol and in environmental matrices also atenolol, has been developed. By use of supercriticalfluid chromatography and the polysaccharide-based Chiralpak(®) IB-3, all four compounds were simultaneously enantiomerically separated (Rs>1.5) within 8min. Detection was performed using tandem mass spectrometry, and to avoid isobaric interference between the co-eluting metoprolol and metoprolol acid, the achiral column Acquity(®) UPC(2) BEH 2-EP was attached ahead of to the chiral column. Carbon dioxide with 18% methanol containing 0.5% (v/v) of the additives trifluoroacetic acid and ammonia in a 2:1 molar ratio were used as mobile phase. A post column make-up flow (0.3mL/min) of methanol containing 0.1% (v/v) formic acid was used to enhance the positive electrospray ionization. Detection was carried out using a triple quadrupole mass spectrometer operating in the selected reaction monitoring mode, using one transition per analyte and internal standard. The method was successfully applied for monitoring the enantiomeric fraction change over time in a laboratory scale wetland degradation study. It showed good precision, recovery, sensitivity and low effect of the sample matrix.

The optimisation of focused ultrasound extraction and supercriticalfluid extraction of volatile oils and cannabinoids from marihuana has been accomplished by experimental design approach. On the one hand, the focused ultrasound extraction method of volatile compounds and cannabinoids was studied based on the optimisation of cyclohexane and isopropanol solvent mixtures, and the instrumental variables. The optimal working conditions were finally fixed at isopropanol/cyclohexane 1:1 mixture, cycles (3 s(-1)), amplitude (80%) and sonication time (5 min). On the other hand, the supercriticalfluid extraction method was optimised in order to obtain a deterpenation of the plant and a subsequent cannabinoid extraction. For this purpose, pressure, temperature, flow and co-solvent percentage were optimised and the optimal working conditions were set at 100 bar, 35°C, 1 mL/min, no co-solvent for the terpenes and 20% of ethanol for the cannabinoids. Based on the retention time locking GC-MS analysis of the supercriticalfluid extracts the classification of the samples according to the type of plant, the growing area and season was attained. Finally, three monoterpenes and three cannabinoids were quantified in the ranges of 0.006-6.2 μg/g and 0.96-324 mg/g, respectively.

Two fractions (S1 and S2) of an oregano (Origanum vulgare) extract obtained by supercriticalfluid extraction have been used to test anti-inflammatory effects on activated human THP-1 cells. The main compounds present in the supercritical extract fractions of oregano were trans-sabinene hydrate, thymol and carvacrol. Fractions toxicity was assessed using the mitochondrial-respiration-dependent 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium (MTT) reduction method for several concentrations during 24 and 48 h of incubation. Concentrations higher than 30 microg/mL of both supercritical S1 and S2 oregano fractions caused a reduction in cell viability in a dose-dependent manner. Oxidized-LDLs (oxLDLs) activated THP-1 macrophages were used as cellular model of atherogenesis and the release/secretion of cytokines (TNT-alpha, IL-1beta, IL-6 and IL-10) and their respective mRNA expressions were quantified both in presence or absence of supercritical oregano extracts. The results showed a decrease in pro-inflammatory TNF-alpha, IL-1beta and IL-6 cytokines synthesis, as well as an increase in the production of anti-inflammatory cytokine IL-10. These results may suggest an anti-inflammatory effect of oregano extracts and their compounds in a cellular model of atherosclerosis.

A method using derivatization and supercriticalfluid extraction coupled with gas chromatography was developed for the analysis of dimethylarsinate, monomethylarsonate and inorganic arsenic simultaneously in solid matrices. Thioglycolic acid n-butyl ester was used as a novel derivatizing reagent. A systematic discussion was made to investigate the effects of pressure, temperature, flow rate of the supercritical CO2 , extraction time, concentration of the modifier, and microemulsion on extraction efficiency. The application for real environmental samples was also studied. Results showed that thioglycolic acid n-butyl ester was an effective derivatizing reagent that could be applied for arsenic speciation. Using methanol as modifier of the supercritical CO2 can raise the extraction efficiency, which can be further enhanced by adding a microemulsion that contains Triton X-405. The optimum extraction conditions were: 25 MPa, 90°C, static extraction for 10 min, dynamic extraction for 25 min with a flow rate of 2.0 mL/min of supercritical CO2 modified by 5% v/v methanol and microemulsion. The detection limits of dimethylarsinate, monomethylarsonate, and inorganic arsenic in solid matrices were 0.12, 0.26, and 1.1 mg/kg, respectively. The optimized method was sensitive, convenient, and reliable for the extraction and analysis of different arsenic species in solid samples.

Full Text Available The advancement of alternative energy is primarily catalyzed by the negative environmental impacts and energy depletion caused by the excessive usage of fossil fuels. Biodiesel has emerged as a promising substitute to petrodiesel because it is biodegradable, less toxic, and reduces greenhouse gas emission. Apart from that, biodiesel can be used as blending component or direct replacements for diesel fuel in automotive engines. A diverse range of methods have been reported for the conversion of renewable feedstocks (vegetable oil or animal fat into biodiesel with transesterification being the most preferred method. Nevertheless, the cost of producing biodiesel is higher compared to fossil fuel, thus impeding its commercialization potentials. The limited source of reliable feedstock and the underdeveloped biodiesel production route have prevented the full-scale commercialization of biodiesel in many parts of the world. In a recent development, a new technology that incorporates monoliths as support matrices for enzyme immobilization in supercritical carbon dioxide (SC-CO2 for continuous biodiesel production has been proposed to solve the problem. The potential of SC-CO2 system to be applied in enzymatic reactors is not well documented and hence the purpose of this review is to highlight the previous studies conducted as well as the future direction of this technology.

Silver nanoparticle-decorated graphene nanocomposites were synthesized by a facile chemical reduction approach with the assistance of supercritical CO2 (ScCO2). The silver nanoparticles with diameters of 2-16 nm are uniformly distributed and firmly anchored on graphene nanosheets. The tribological properties of the as-synthesized nanocomposites as lubricant additives in engine oil were investigated by a four-ball tribometer. The engine oil with 0.06~0.10 wt.% Sc-Ag/GN nanocomposites displays remarkable lubricating performance, superior than the pure engine oil, the engine oil containing zinc dialkyl dithiophosphate (ZDDP), as well as the oil dispersed with the single nanomaterial of graphene oxides (GOs) and nano-Ag particles alone. The remarkable lubricating behaviors of Sc-Ag/GN probably derive from the synergistic interactions of nano-Ag and graphene in the nanocomposite and the action of the formed protective film on the contact balls. The anchored nano-Ag particles on graphene expand the interlamination spaces of graphene nanosheets and can prevent them from restacking during the rubbing process, resulting in the full play of lubricating activity of graphene. The formed protective film on the friction pairs significantly reduces the surface roughness of the sliding balls and hence preventing them from direct interaction during the sliding process.

In this study, we evaluated the influence of supercritical carbon dioxide (scCO2) spray drying conditions, in the absence of organic solvent, on the ability to produce dry protein/trehalose formulations at 1:10 and 1:4 (w/w) ratios. When using a 4L drying vessel, we found that decreasing the solution flow rate and solution volume, or increasing the scCO2 flow rate resulted in a significant reduction in the residual water content in dried products (Karl Fischer titration). The best conditions were then used to evaluate the ability to scale the scCO2 spray drying process from 4L to 10L chamber. The ratio of scCO2 and solution flow rate was kept constant. The products on both scales exhibited similar residual moisture contents, particle morphologies (SEM), and glass transition temperatures (DSC). After reconstitution, the lysozyme activity (enzymatic assay) and structure (circular dichroism, HP-SEC) were fully preserved, but the sub-visible particle content was slightly increased (flow imaging microscopy, nanoparticle tracking analysis). Furthermore, the drying condition was applicable to other proteins resulting in products of similar quality as the lysozyme formulations. In conclusion, we established scCO2 spray drying processing conditions for protein formulations without an organic solvent that holds promise for the industrial production of dry protein formulations.

Silver nanoparticle-decorated graphene nanocomposites were synthesized by a facile chemical reduction approach with the assistance of supercritical CO2 (ScCO2). The silver nanoparticles with diameters of 2–16 nm are uniformly distributed and firmly anchored on graphene nanosheets. The tribological properties of the as-synthesized nanocomposites as lubricant additives in engine oil were investigated by a four-ball tribometer. The engine oil with 0.06~0.10 wt.% Sc-Ag/GN nanocomposites displays remarkable lubricating performance, superior than the pure engine oil, the engine oil containing zinc dialkyl dithiophosphate (ZDDP), as well as the oil dispersed with the single nanomaterial of graphene oxides (GOs) and nano-Ag particles alone. The remarkable lubricating behaviors of Sc-Ag/GN probably derive from the synergistic interactions of nano-Ag and graphene in the nanocomposite and the action of the formed protective film on the contact balls. The anchored nano-Ag particles on graphene expand the interlamination spaces of graphene nanosheets and can prevent them from restacking during the rubbing process, resulting in the full play of lubricating activity of graphene. The formed protective film on the friction pairs significantly reduces the surface roughness of the sliding balls and hence preventing them from direct interaction during the sliding process.

To improve drilling performance, a drilling fluid is selected based on one or more criteria and to have at least one target characteristic. Drilling equipment is used to drill a wellbore, and the selected drilling fluid is provided into the wellbore during drilling with the drilling equipment. The at least one target characteristic of the drilling fluid includes an ability of the drilling fluid to penetrate into formation cuttings during drilling to weaken the formation cuttings.

Ground cumin is used as a flavoring agent in a number of ethnic cuisines. The chemical entities, which primarily establish its characteristically pungent flavor, are found in the volatile oil of cumin. Fixed oils and carbohydrates tend to round out the harshness of the volatile oil components. However, the quantity of volatile oil is commonly the measure of the quality of this spice. For several decades, the spice industry has used a classical distillation procedure for the determination of volatile oil in cumin and other spices. However, the method is cumbersome and requires nearly 8 h to complete. Supercriticalfluid extraction with capillary gas chromatography-flame ionization detection is utilized in the formulation of a rapid, accurate, and specific method for the determination of volatile oil in ground cumin. Samples are extracted in a static-dynamic mode with CO2 at 550 bar and 100 degrees C. Toluene is used as a static modifier addition. The extracted volatile oil, collected in toluene, is analyzed directly using tetradecane as the internal standard. Integration is performed as grouped peaks to include all chemical entities found in cumin volatile oil recovered from the official distillation procedure. Results from this procedure compare favorably with those obtained by the official procedure (coefficient of correlation = 0.995, 24 samples).

Combustion-derived PAHs are strongly sorbed to their particulate carrier (i.e., soot, charcoal), and therefore, very slow desorption kinetics of the chemicals might be anticipated. Measurements are however lacking, because conventional methods (Tenax, XAD, gas-purging) fail to accurately determine desorption kinetics due to practical problems. In this study, we used a mild supercriticalfluid extraction (SFE) method, which mimics desorption into water and circumvents these problems, to quantify desorption kinetics of 13 native PAHs from pure charcoal, coal, and four types of soot. The results show that generally only very small PAH fractions are released. Desorption behavior was, however, not related to common sorbent/sorbate characteristics. Two-site model-derived "fast desorbing fractions" were water measured from 10(-7) to 10(-5) h(-1). These data suggest that desorption of coal and combustion-derived PAHs can be even slower than the "very slow" desorption observed in sediments. Estimated time scales required for removal of pyrogenic PAHs from these extremely slow sites into water amount to several millennia. Our results imply reduced chemical risks for soot and soot-like materials, casting doubts on current risk assessment procedures and environmental quality standards of pyrogenic PAHs.

Kenaf (Hibiscus cannabinus) from the family Malvaceae, is a valuable fiber plant native to India and Africa and is currently planted as the fourth commercial crop in Malaysia. Kenaf seed oil contains alpha-linolenic acid, phytosterol such as β -sitosterol, vitamin E, and other antioxidants with chemopreventive properties. Kenaf seeds oil (KSO) was from supercritical carbon dioxide extraction fluid (SFE) at 9 different permutations of parameters based on range of pressures from 200 to 600 bars and temperature from 40 to 80°C. They were 200/40, 200/60, 200/80, 400/40, 400/60, 400/80, 600/40, 600/60, and 600/80. Extraction from 9 parameters of KSO-SFE was screened for cytotoxicity towards human colorectal cancer cell lines (HT29) and mouse embryonic fibroblast (NIH/3T3) cell lines using MTS assay. KSO-SFE at 600/40 showed the strongest cytotoxicity towards HT29 with IC50 of 200 µg/mL. The IC50 for NIH/3T3 was not detected even at highest concentration employed. Cell cycle analysis showed a significant increase in the accumulation of KSO-SFE-treated cells at sub-G1 phase, indicating the induction of apoptosis by KSO-SFE. Further apoptosis induction was confirmed by Annexin V/PI and AO/PI staining.

The main constituents,senkyunolide A,Zligustilide,neocnidilide,3-butylphthalide,and ligustilide dimers,in supercritical CO2 fluid extracts of Rhizoma Chuanxiong,a popular Chinese traditional medicine,have been identified and characterized by high performance liquid chromatography tandem mass spectrometry.Separations were carded out on an Agilent (ECLIPSE XDB) C18 analytical column by gradient elution with 0.25% acetic acid and methanol (containing 0.25% acetic acid).An Agilent 1100 series LC/MSD XCT system was operated under positive ESI and auto MS/MS modes for mass spectrometric analysis.Collision-induced dissociation (CID) fragmentations of these phthalides have been investigated and elucidated.Phthalides have primarily undergone two ESI CID pathways:side-chain cleavage with losses of alkenes and ring-opening with eliminations of H2O followed by losses of CO.Direct neutral loss of CO has not been observed.Sodium adduct ions have demonstrated completely different CID pathways.

A series of TiO2-SnO2 nano-sized composite photo-catalysts containing Sn (9.3%～30.1%) were prepared from TiCl4and SnCl4.5H2O by using sol-gel, supercriticalfluid dry and solid-phase reaction (SCFD) combination technology.Characterizations with X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed that, in addition to anatase type TiO2, a new active phase (Ti, Sn)O2 (with particle size of 2.0～4.3 nm) formed, and there were no SnO2 crystals observed in the range of the doping concentration studied. Photo-catalytic reaction of phenol was used as a model reaction to evaluate the catalytic activities of the obtained catalysts. Compared with pure TiO2 or Ti-Sn catalyst prepared with general sol-gel method, Ti-Sn nanocomposite photo-catalyst thus obtained showed significant improvement in catalytic activity. The photo-catalytic degradation rate of phenol could reach as high as 93.5% after 7 h. The preparation conditions of the new phase (Ti, Sn)O2 were investigated and its catalytic mechanism was proposed. The photo-catalytic particles prepared using SCFD combination technology exhibited small particle size, large surface area and high activity.

Numerical algorithm is developed for modelling non-linear mass transfer process in supercriticalfluid extraction (SFE). The ground raw material is considered as polydisperse, characterized by discrete number of effective particle fractions. Two continuous interacting counterparts separated by permeable membrane are distinguished in plant material build-up. The apoplast plays role of transport channels during extraction, and symplast contains extractable oil. The complete SFE model is non-linear as a result of non-linearity of oil dissolution kinetics. The computational scheme is based on the finite-volume approximation method and Thomas elimination procedure. The resulting system of algebraic equations is solved iteratively. Special attention is paid to polydisperse substrates, when particle scale characteristics of all fractions interact with each other through pore phase concentration on the vessel scale. Stability of the developed algorithm is demonstrated in numerical tests. Special iterative procedure guarantees a monotonic decrease of oil content in individual particles of substrate. It is also shown that in the limit of the so-called shrinking core approach the number of mesh nodes on a particle scale should be increased.

Full Text Available A novel biocomposite material from a stereocomplex of poly (L-lactide-co-ε-caprolactone (PLLCL and poly (D-lactide-co-ε-caprolactone (PDLCL and inorganic tricalcium phosphate (TCP was prepared by supercriticalfluid method. Both pristine and poly (L-lactide-grafted-TCP (PLLA-g-TCP were used. PLLA-g-TCP was produced by ringopening polymerization of L-lactide in the presence of surface-activated TCP. Infrared (IR spectroscopy and scanning electron microscopic (SEM images confirm the attachment of PLLA onto the activated TCP surface. The stereocomplex formation of biocomposite was confirmed by differential scanning calorimetry (DSC and wide-angle X-ray diffraction (WAXD. The biocomposite containing PLLA-g-TCP has higher stereocomplex degree and more homogeneous TCP distribution compared to the biocomposite containing pristine TCP. The presence of PLLA-g-TCP in the stereocomplex PLLCLPDLCL (s-PDLCL enhance the stereocomplex degree up to a certain content and also supports the homogeneous TCP dispersion in the stereocomplex matrix. These phenomena support the improvement in mechanical properties of the s-PDLCL composite the optimum content of PLLA-g-TCP being 10%. The biocomposites containing TCP materials are promising materials for biomedical application, especially for bone tissue engineering.

A new interface was designed to enable the coupling of reversed phase liquid chromatography (RPLC) and supercriticalfluid chromatography (SFC). This online two-dimensional chromatographic system utilizing RPLC in the first dimension and SFC in the second was developed to achieve simultaneous achiral and chiral analysis of pharmaceutical compounds. The interface consists of an eight-port, dual-position switching valve with small volume C-18 trapping columns. The peaks of interest eluting from the first RPLC dimension column were effectively focused as sharp concentration pulses on small volume C-18 trapping column/s and then injected onto the second dimension SFC column. The first dimension RPLC separation provides the achiral purity result, and the second dimension SFC separation provides the chiral purity result (enantiomeric excess). The results are quantitative enabling simultaneous achiral, chiral analysis of compounds. The interface design and proof of concept demonstration are presented. Additionally, comparative studies to conventional SFC and case studies of the applications of 2D LC-SFC in pharmaceutical analysis is presented.

The effect of supercriticalfluid extraction (SFE) fractionation of three oil fractions (1st, 2nd, 3rd fraction) on the fatty acid composition and antioxidant activity of oils from two cultivars of cantaloupe were investigated. Rock melon oil (RMO) and Golden Langkawi oil (GLO) were extracted using SFE and the major fatty acids for both cultivars were linoleic, oleic, palmitic, and stearic acid. The SFA decreased from 15.78 to 14.14% in RMO 1st fraction, and MUFA decreased from 18.30 to 16.56% in RMO 2nd fraction, while PUFA increased from 65.9 to 69.30% in RMO 3rd fraction. On the other hand SFA decreased from 16.35 to 13.91% in GLO 1{sup s}t fraction, and MUFA decreased from 17.50 to 15.57% in GLO 2nd fraction, while PUFA increased from 66.15 to 70.52% in GLO 3rd fraction. The different fractions of the two oils showed high antioxidant activity in reducing the oxidation of {beta}-carotene in beta-carotene bleaching assay (BCB) and the quenching of 1,1-diphenyl-2-picrylhydrazyl (DPPH). (Author) 41 refs.

Full Text Available Kenaf (Hibiscus cannabinus from the family Malvaceae, is a valuable fiber plant native to India and Africa and is currently planted as the fourth commercial crop in Malaysia. Kenaf seed oil contains alpha-linolenic acid, phytosterol such as β-sitosterol, vitamin E, and other antioxidants with chemopreventive properties. Kenaf seeds oil (KSO was from supercritical carbon dioxide extraction fluid (SFE at 9 different permutations of parameters based on range of pressures from 200 to 600 bars and temperature from 40 to 80°C. They were 200/40, 200/60, 200/80, 400/40, 400/60, 400/80, 600/40, 600/60, and 600/80. Extraction from 9 parameters of KSO-SFE was screened for cytotoxicity towards human colorectal cancer cell lines (HT29 and mouse embryonic fibroblast (NIH/3T3 cell lines using MTS assay. KSO-SFE at 600/40 showed the strongest cytotoxicity towards HT29 with IC50 of 200 µg/mL. The IC50 for NIH/3T3 was not detected even at highest concentration employed. Cell cycle analysis showed a significant increase in the accumulation of KSO-SFE-treated cells at sub-G1 phase, indicating the induction of apoptosis by KSO-SFE. Further apoptosis induction was confirmed by Annexin V/PI and AO/PI staining.

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercriticalfluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions.

In this study, the thermal denaturation mechanism and secondary structures of two types of human insulin nanoparticles produced by a process of solution-enhanced dispersion by supercriticalfluids using dimethyl sulfoxide (DMSO) and ethanol (EtOH) solutions of insulin are investigated using spectroscopic approaches and molecular dynamics calculations. First, the temperature-dependent IR spectra of spherical and rod-shaped insulin nanoparticles prepared from DMSO and EtOH solution, respectively, are analyzed using principal component analysis (PCA) and 2D correlation spectroscopy to obtain a deeper understanding of the molecular structures and thermal behavior of the two insulin particle shapes. All-atom molecular dynamics (AAMD) calculations are performed to investigate the influence of the solvent molecules on the production of the insulin nanoparticles and to elucidate the geometric differences between the two types of nanoparticles. The results of the PCA, the 2D correlation spectroscopic analysis, and the AAMD calculations clearly reveal that the thermal denaturation mechanisms and the degrees of hydrogen bonding in the spherical and rod-shaped insulin nanoparticles are different. The polarity of the solvent might not alter the structure or function of the insulin produced, but the solvent polarity does influence the synthesis of different shapes of insulin nanoparticles.

This work describes the development of two methods involving supported liquid extraction (SLE) sample treatment followed by ultra-high performance liquid chromatography or ultra-high performance supercriticalfluid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS and UHPSFC-MS/MS) for the screening of 43 anabolic agents in human urine. After evaluating different stationary phases, a polar-embedded C18 and a diol columns were selected for UHPLC-MS/MS and UHPSFC-MS/MS, respectively. Sample preparation, mobile phases and MS conditions were also finely tuned to achieve highest selectivity, chromatographic resolution and sensitivity. Then, the performance of these two methods was compared to the reference routine procedure for steroid analyses in anti-doping laboratories, which combines liquid-liquid extraction (LLE) followed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). For this purpose, urine samples spiked with the compounds of interest at five different concentrations were analyzed using the three analytical platforms. The retention and selectivity of the three techniques were very different, ensuring a good complementarity. However, the two new methods displayed numerous advantages. The overall procedure was much faster thanks to high throughput SLE sample treatment using 48-well plates and faster chromatographic analysis. Moreover, the highest sensitivity was attained using UHPLC-MS/MS with 98% of the doping agents detected at the lowest concentration level (0.1ng/mL), against 76% for UHPSFC-MS/MS and only 14% for GC-MS/MS. Finally, the weakest matrix effects were obtained with UHPSFC-MS/MS with 76% of the analytes displaying relative matrix effect between -20 and 20%, while the GC-MS/MS reference method displayed very strong matrix effects (over 100%) for all of the anabolic agents.

Lycopene, a carotenoid linked to protection against certain forms of cancer, is found in produce such as papaya, red-fleshed tomatoes, grapefruit and watermelon. The preparation of a supercritical CO2 (SC-CO2) watermelon-lycopene extract could serve as a food grade source of this carotenoid. This study established preliminary conditions for enhancing SC-CO2 extraction of lycopene from watermelon. Freeze-dried watermelon was extracted with SC-CO2 and ethanol as an organic co-solvent. The lycopene concentration was determined by HPLC, with absorbance measured at 503 nm. In an initial set of experiments, the effects of extraction temperature (70-90 degrees C), pressure (20.7-41.4 MPa) and co-solvent ethanol addition (10-15%) were evaluated. A lycopene yield of 38 microg per gram of wet weight was obtained at 70 degrees C, 20.7 MPa, and 15% by volume ethanol. The extraction of fresh (non-freeze-dried) watermelon yielded 103+/-6 microg lycopene per gram fresh fruit weight. Of the parameters tested, temperature had the most effect on lycopene yield. Thus, in another set of experiments, the temperature was varied from 60-75 degrees C at an extraction pressure of 20.7 MPa in the presence of 15% ethanol. Studies showed that freeze-dried watermelon flesh loses lycopene in storage. In accounting for lycopene storage losses, lycopene yields at 60 degrees C extraction temperature were 14% greater than those obtained at 70 degrees C.

Annonaceous acetogenins (ACGs) isolated from Annonaceae plants exhibited a broad range of biological bioactivities such as cytotoxic, antitumoral, antiparasitic, pesticidal and immunosuppresive activities. However, their structures were liable to change at more than 60°C and their extraction yields were low using traditional organic solvent extraction. In the present study, all samples from Annona genus plant seeds were extracted by supercritical carbon dioxide under optimized conditions and a high-performance liquid chromatography (HPLC) method was established for simultaneously determining ten ACGs. All of the ten compounds were simultaneously separated on reversed-phase C18 column (250 mm × 4.6 mm, 5 μm) with the column temperature at 30°C. The mobile phase was composed of (A) methanol and (B) distilled water, the flow rate was 1.0 ml/min and the detection wavelength was set at 220 nm. All calibration curves showed good linear regression (γ>0.9995) within the test range. The established method showed good precision and accuracy with overall intra-day and inter-day variations of 0.99-2.56% and 1.93-3.65%, respectively, and overall recoveries of 95.16-105.01% for the ten compounds analyzed. The established method can be applied to evaluate the intrinsic quality of Annonaceae plant seeds. The determination results recover the content-variation regularities of various ACGs in different species, which are helpful to choose the good-quality Annonaceae plant seeds for anticancer lead compound discovery.

This contribution proposes an enzyme-assisted eco-friendly process for the extraction of non-extractable polyphenols (NEPPs) from black tea leftover (BTLO), an underutilized tea waste. BTLO hydrolyzed with various enzyme formulations was extracted using supercritical carbon dioxide and ethanol as co-solvent (SC-CO2 + EtOH). A conventional solvent extraction (CSE) was performed using EtOH + H2O (80:20, v/v) for comparison purposes. The results revealed that hydrolysis of BTLO with 2.9% (w/w) kemzyme at 45 °C and pH 5.4 for 98 min improved the liberation of NEPPs offering 5-fold higher extract yield (g/100 g) as compared with non-treated BTLO. In vitro antioxidant evaluation and LC-MS characterization of extracts revealed the presence of phenolic acids (mainly caffeic and para-coumaric acid) of high antioxidant value. Scanning electron micrograph of the hydrolyzed BTLO samples indicated noteworthy changes in the ultrastructure of BTLO. Moreover, polyphenol extracts obtained by SC-CO2 + EtOH extraction were found to be cleaner and richer in polyphenols as compared to CSE. The devised enzyme-assisted SC-CO2 + EtOH extraction process in the present work can be explored as an effective biotechnological mean for the optimal recovery of antioxidant polyphenols. Graphical abstract Enzymatic pretreatment can effectively liberate non-extractable polyphenols (NEPPs) while hydrolyzing the cellulosic and hemicellulosic framework of black tea left overs (BTLO).

Physical mechanisms of thermally driven rotating fluids are important for a large number of geophysical problems, e.g. to explain the convection of the Earth's liquid outer core. Objective of the 'GeoFlow' experiment is to study stability, pattern formation, and transition to chaos of thermal convection in fluid-filled concentric, co-axially rotating spheres. This experiment is integrated in the Fluid Science Laboratory of the European COLUMBUS module on International Space Station. Fluid dynamics of the experiment was predicted with numerical simulations by means of a spectral code. In the non-rotating case the onset of convection bifurcated into steady fluid flow. Here patterns of convection showed co-existing states with axisymmetric, cubic and pentagonal modes. Transition to chaos was in the form of sudden onset. For the thermal convection in rotating spheres the onset of first instability showed an increase of modes for higher parameter regime. Transition was from steady via periodic to chaotic behaviour. Convection patterns of the experiment are observed with the Wollaston shearing interferometry. Images are in terms of interferograms with fringe patterns corresponding to special convective flows. A first glance at the images showed the classification of sub- and supercritical flow regimes. Aligned with numerical data a shift between experiment and numerical simulation was identified. Identification of convection patterns in interferograms was demonstrated for the example of a supercritical flow.

Chromatography techniques usually use a single state in the mobile phase, such as liquid, gas, or supercriticalfluid. Chromatographers manage one of these techniques for their purpose but are sometimes required to use multiple methods, or even worse, multiple techniques when the target compounds have a wide range of chemical properties. To overcome this challenge, we developed a single method covering a diverse compound range by means of a "unified" chromatography which completely bridges supercriticalfluid chromatography and liquid chromatography. In our method, the phase state was continuously changed in the following order; supercritical, subcritical and liquid. Moreover, the gradient of the mobile phase starting at almost 100% CO2 was replaced with 100% methanol at the end completely. As a result, this approach achieved further extension of the polarity range of the mobile phase in a single run, and successfully enabled the simultaneous analysis of fat- and water-soluble vitamins with a wide logP range of -2.11 to 10.12. Furthermore, the 17 vitamins were exceptionally separated in 4min. Our results indicated that the use of dense CO2 and the replacement of CO2 by methanol are practical approaches in unified chromatography covering diverse compounds. Additionally, this is a first report to apply the novel approach to unified chromatography, and can open another door for diverse compound analysis in a single chromatographic technique with single injection, single column and single system.

A theory that explains the operating pressures where liquid injection processes transition from exhibiting classical two-phase spray atomization phenomena to single-phase diffusion-dominated mixing is presented. Imaging from a variety of experiments have long shown that under certain conditions, typically when the pressure of the working fluid exceeds the thermodynamic critical pressure of the liquid phase, the presence of discrete two-phase flow processes become diminished. Instead, the classical gas-liquid interface is replaced by diffusion-dominated mixing. When and how this transition occurs, however, is not well understood. Modern theory still lacks a physically based model to quantify this transition and the precise mechanisms that lead to it. In this paper, we derive a new model that explains how the transition occurs in multicomponent fluids and present a detailed analysis to quantify it. The model applies a detailed property evaluation scheme based on a modified 32-term Benedict-Webb-Rubin equation of state that accounts for the relevant real-fluid thermodynamic and transport properties of the multicomponent system. This framework is combined with Linear Gradient Theory, which describes the detailed molecular structure of the vapor-liquid interface region. Our analysis reveals that the two-phase interface breaks down not necessarily due to vanishing surface tension forces, but due to thickened interfaces at high subcritical temperatures coupled with an inherent reduction of the mean free molecular path. At a certain point, the combination of reduced surface tension, the thicker interface, and reduced mean free molecular path enter the continuum length scale regime. When this occurs, inter-molecular forces approach that of the multicomponent continuum where transport processes dominate across the interfacial region. This leads to a continuous phase transition from compressed liquid to supercritical mixture states. Based on this theory, a regime diagram for

Human activity is constantly causing environmental problems due to production and release of numerous chemicals. A group of compounds of special concern is persistent organic pollutants (POP). These toxic, lipophilic chemicals have a high chemical and biological stability, and tend to accumulate in the lipid phase of living organisms. A major sink for POPs are sediments, and consequently these are important for the distribution of POPs in the aquatic environment. Traditionally, determination of POPs relay on exhaustive extraction using liquid extraction techniques (e.g. Soxhlet extraction developed in the late 19th century) followed by gas chromatographic analysis. Since liquid-solid extraction normally requires large volumes of organic solvents in combination with long extraction times and extract clean-up, there has been an increasing demand for improved technology. This should result in reduced organic solvent consumption and sample preparation time, at the same time improving the environment and cutting costs for POP monitoring. In this thesis two modern techniques with capability of fulfilling at least one of these goals have been investigated: (1) SupercriticalFluid Extraction (SFE), and (2) Accelerated Solvent Extraction (ASE). Polychlorinated biphenyls (PCBs) were chosen as model compounds in all experiments performed on environmental matrices, since they cover a relatively large range of physiochemical parameters. Important parameters influencing the overall extraction efficiency in ASE and SFE, are discussed and illustrated for a large number of sediments. It was demonstrated that, by careful consideration of the experimental parameters, both techniques are capable of replacing old methods such as Soxhlet extraction. ASE is somewhat faster than SFE, but the extracts generated in SFE are much cleaner and can be analyzed without sample clean-up. Consequently the overall sample preparation time may be substantially lower using SFE. However, ASE is important

New hyphenated technique for the extraction and determination of isoflavones in sea and freshwater algae and cyanobacteria was developed. The method consists of sonication sample pretreatment, extraction by supercritical CO(2) modified by 3% (v/v) of MeOH/H(2)O mixture (9:1, v/v) at 35 MPa and 40°C for 60 min, fast chromatography analysis by the means of Agilent 1200 Series Rapid Resolution and MS/MS determination. Agilent 1200 Series RRLC was used with Zorbax SB-CN chromatographic column (100 mm × 2.1mm, particle size 3.5 μm), 3μl injection volume, mobile phase consisting of 0.2% (v/v) acetic acid in water (solvent A) and acetonitrile (solvent B) and used with linear gradient (30% B at 0 min, from 0 min to 3 min up to 50% B, from 3 to 6 min up to 80% B and from 6 to 10 min down to 30% B). The flow-rate was 0.4 mL/min, column oven temperature 35°C. MS detector Agilent Technologies 6460 Triple quadrupole LC/MS with Agilent Jet Stream was used in a negative ESI mode under following conditions: gas temperature 350°C, gas flow 13 L/min, nebulizer gas pressure 50 psi, sheath gas temperature 400°C, sheath gas flow 12L/min, capillary voltage was 4 kV. Samples were analysed in the multiple reaction monitoring (MRM) mode. Eight isoflavone compounds were found for the first time in seven real samples of sea algae and in three control samples of freshwater algae and cyanobacteria. Usual optimisation study of extraction parameters was performed. Pressure and temperature optima for algae matrix are different from those obtained sooner for other matrices for most of the analytes, but the results of modifier optimisation study are in good accordance with those obtained sooner for spiked samples and red clover matrix. It seems that matrix has very small or no effect on the modifier selection. Two different approaches of sonication pretreatment were tested: sonication bath and the thorn instrument. In longer extraction time experiments, thorn sonication was more efficient

This paper describes a comparative study of the gravimetric versus hydrolysis/derivatization/gas chromatography-mass spectrometry determination of fat in infant formula. Fat was extracted using supercritical carbon dioxide modified with a small amount of ethanol, the extract was weighed, and the total fat was determined gravimetrically. Subsequently, another sample of the supercriticalfluid fat extract was hydrolyzed to yield free fatty acids, which were converted to their methyl ester derivatives (FAMEs). Quantification was performed by GC-MS. NIST Standard Reference Material (SRM-1846) was used to validate both fat determination methods. Results showed that the gravimetric average percent fat was 26.86%, whereas the GC-MS method yielded 24.64%. Some peaks were detected in the ion chromatogram from the GC-MS that were identified as nonfatty acids such as aldehydes, which may account for the higher percentage fat measured as weight of extract rather than measured as FAMEs expressed as triglycerides.

Problems of flow of viscoelastic liquids were considered emphasizing the issues generated by the fluid's elasticity, which gives rise to hyperbolicity and waves. These studies are summarized with many studies of drag reductions using water lubrication, riblets, and polymers. These studies will be summarized in my new book (with Yuriko Renardy): Two-Fluid Dynamics. We started a computational numerical effort aimed at studying the motion of particles in fluids using the Navier Stokes equations and the particle equations of motion.

Full Text Available Azacitidine is widely used for the treatment of myelodysplastic syndromes (MDS and acute myelogenous leukaemia (AML. The analysis of azacitidine in biological samples is subject to interference by endogenous compounds. Previously reported high-performance liquid chromatography/tandem mass spectrometric (HPLC-MS/MS bioanalytical assays for azacitidine suffer from expensive sample preparation procedures or from long separation times to achieve the required selectivity. Herein, supercriticalfluid chromatography with tandem mass spectrometry (SFC-MS/MS was explored as a more promising technique for the selective analysis of structure-like or chiral drugs in biological matrices. In this study, a simple, rapid and specific SFC/MS/MS analytical method was developed for the determination of azacitidine levels in rat plasma. Azacitidine was completely separated from the endogenous compounds on an ACQUITY UPLC™ BEH C18 column (100 mm × 3.0 mm, 1.7 μm; Waters Corp., Milford, MA, USA using isocratic elution with CO2/methanol as the mobile phase. The single-run analysis time was as short as 3.5 min. The sample preparation for protein removal was accomplished using a simple methanol precipitation method. The lower limit of quantification (LLOQ of azacitidine was 20 ng/mL. The intra-day and inter-day precisions were less than 15%, and the relative error (RE was within ±15% for the medium- and high-concentration quality control (QC samples and within ±20% for the low-concentration QC samples. Finally, the developed method was successfully applied to a pharmacokinetic study in rats following the intravenous administration of azacitidine.

A low-waste technology for the reprocessing of spent nuclear fuel (SNF) has been developed recently, which involves the conversion of actinide and lanthanide oxides with liquid N{sub 2}O{sub 4} into their nitrates followed by supercriticalfluid extraction of the nitrates. The possibility of the reprocessing of SNF from high-temperature gas-cooled reactors (HTGRs) with nitrate conversion and supercriticalfluid extraction is a current area of research in China. Here, a UO{sub 2}-CeO{sub 2} solid solution was prepared as a surrogate for a UO{sub 2}-PuO{sub 2} solid solution, and the recovery of U and Ce from the UO{sub 2}-CeO{sub 2} solid solution with liquid N{sub 2}O{sub 4} and supercritical CO{sub 2} containing tri-n-butyl phosphate (TBP) was investigated. The UO{sub 2}-CeO{sub 2} solid solution prepared by electrolytic reduction-coprecipitation method had square plate microstructures. The solid solution after heat treatment was completely converted into nitrates with liquid N{sub 2}O{sub 4}. The XRD pattern of the nitrates was similar to that of UO{sub 2}(NO{sub 3}){sub 2} . 3H{sub 2}O. After 120 min of online extraction at 25 MPa and 50 , 99.98% of the U and 98.74% of the Ce were recovered from the nitrates with supercritical CO{sub 2} containing TBP. The results suggest a promising potential technology for the reprocessing of SNF from HTGRs. (orig.)

A new supercritical extraction methodology was applied to extract azadirachtin A (AZA-A) from neem seed kernels. Supercritical and liquid carbon dioxide (CO(2)) were used as extractive agents in a three-separation-stage supercritical pilot plant. Subcritical conditions were tested too. Comparisons were carried out by calculating the efficiency of the pilot plant with respect to the milligrams per kilogram of seeds (ms/mo) of AZA-A extracted. The most convenient extraction was gained using an ms/mo ratio of 119 rather than 64. For supercritical extraction, a separation of cuticular waxes from oil was set up in the pilot plant. HPLC and electrospray mass spectroscopy were used to monitor the yield of AZA-A extraction.

of processmodels and constraints 2) selection of property models, i.e. Penge Robinson equation of state 3)screening of 1965 possible working fluid candidates including identification of optimal process parametersbased on Monte Carlo sampling 4) propagating uncertainty of fluid parameters to the ORC netpower output......This study presents a generic methodology to select working fluids for ORC (Organic Rankine Cycles)taking into account property uncertainties of the working fluids. A Monte Carlo procedure is described as a tool to propagate the influence of the input uncertainty of the fluid parameters on the ORC...

The viability and biological activity of Absidia coerulea in compressed or supercritical CO2 and C2H4 were studied. The specific activity ofAbsidia coerulea in 7.5MPa CO2 and C2H4 at 306K can reach to 23% and 75% respectively, leading to the feasibility of using supercritical C2H4as an alternative to the organic solvent in the hydroxylation of Reichsterin's substance acetate.

The Aeroelastic Prediction Workshop brought together an international community of computational fluid dynamicists as a step in defining the state of the art in computational aeroelasticity. The Rectangular Supercritical Wing (RSW) was chosen as the first configuration to study due to its geometric simplicity, perceived simple flow field at transonic conditions and availability of an experimental data set containing forced oscillation response data. Six teams performed analyses of the RSW; they used Reynolds-Averaged Navier-Stokes flow solvers exercised assuming that the wing had a rigid structure. Both steady-state and forced oscillation computations were performed by each team. The results of these calculations were compared with each other and with the experimental data. The steady-state results from the computations capture many of the flow features of a classical supercritical airfoil pressure distribution. The most dominant feature of the oscillatory results is the upper surface shock dynamics. Substantial variations were observed among the computational solutions as well as differences relative to the experimental data. Contributing issues to these differences include substantial wind tunnel wall effects and diverse choices in the analysis parameters.

A seal assembly for sealing a machine with a first chamber and a second chamber is provided. A rotating shaft extends through the first and second chambers, and rotates therein. The seal assembly has a seal housing, a seal ring and a seal pin. The seal housing is positionable in the machine housing. The seal housing has a seal pocket extending into a fluid side thereof, and a housing receptacle extending into an inner diameter thereof at the seal pocket. The seal ring is positionable in the seal pocket of the seal housing for forming a seal therewith. The seal ring has a ring receptacle extending into an outer diameter thereof. The ring receptacle is positionable adjacent to the housing receptacle for defining a pin hole therebetween. The seal pin is loosely positionable in the pin hole whereby movement about the seal ring is accommodated while preventing rotation thereof.

This study shows the possibility offered by modern ultra-high performance supercriticalfluid chromatography combined with tandem mass spectrometry in doping control analysis. A high throughput screening method was developed for 100 substances belonging to the challenging classes of anabolic agents, hormones and metabolic modulators, synthetic cannabinoids and glucocorticoids, which should be detected at low concentrations in urine. To selectively extract these doping agents from urine, a supported liquid extraction procedure was implemented in a 48-well plate format. At the tested concentration levels ranging from 0.5 to 5 ng/mL, the recoveries were better than 70% for 48-68% of the compounds and higher than 50% for 83-87% of the tested substances. Due to the numerous interferences related to isomers of steroids and ions produced by the loss of water in the electrospray source, the choice of SFC separation conditions was very challenging. After careful optimization, a Diol stationary phase was employed. The total analysis time for the screening assay was only 8 min, and interferences as well as susceptibility to matrix effect (ME) were minimized. With the developed method, about 70% of the compounds had relative ME within the range ±20%, at a concentration of 1 and 5 ng/mL. Finally, limits of detection achieved with the above-described strategy including 5-fold preconcentration were below 0.1 ng/mL for the majority of the tested compounds. Therefore, LODs were systematically better than the minimum required performance levels established by the World anti-doping agency, except for very few metabolites.

The aim of this investigation was to develop a procedure to improve the dissolution and bioavailability of silymarin (SM) by using bile salt-containing liposomes that were prepared by supercriticalfluid technology (ie, solution-enhanced dispersion by supercriticalfluids [SEDS]). The process for the preparation of SM-loaded liposomes containing a bile salt (SM-Lip-SEDS) was optimized using a central composite design of response surface methodology with the ratio of SM to phospholipids (w/w), flow rate of solution (mL/min), and pressure (MPa) as independent variables. Particle size, entrapment efficiency (EE), and drug loading (DL) were dependent variables for optimization of the process and formulation variables. The particle size, zeta potential, EE, and DL of the optimized SM-Lip-SEDS were 160.5 nm, -62.3 mV, 91.4%, and 4.73%, respectively. Two other methods to produce SM liposomes were compared to the SEDS method. The liposomes obtained by the SEDS method exhibited the highest EE and DL, smallest particle size, and best stability compared to liposomes produced by the thin-film dispersion and reversed-phase evaporation methods. Compared to the SM powder, SM-Lip-SEDS showed increased in vitro drug release. The in vivo AUC(0-t) of SM-Lip-SEDS was 4.8-fold higher than that of the SM powder. These results illustrate that liposomes containing a bile salt can be used to enhance the oral bioavailability of SM and that supercriticalfluid technology is suitable for the preparation of liposomes.

Full Text Available A novel catalyst structure for continuous growth of nanocarbon fibers is proposed. In this structure, catalyst nanofibers are embedded in a membrane that separates the growth ambient into carbon-supplying and carbon-precipitating environments. The catalyst nanofibers pierce through the membrane so that carbon source gas is supplied only to one end of the catalyst fibers and nanocarbon fibers grow continuously at the other end. To realize this structure, self-supporting anodized alumina was used as a membrane, and its nano-through-holes were filled with catalyst Ni in supercritical CO2 fluid. Direct carbon growth from the Ni nanofibers was confirmed using this catalyst structure.

Volatile oil from the root bark of Oplopanax horridus is regarded to be responsible for the clinical uses of the title plant as a respiratory stimulant and expectorant. Therefore, a supercriticalfluid extraction method was first employed to extract the volatile oil from the roots bark of O. horridus, which was subsequently analyzed by GC/MS. Forty-eight volatile compounds were identified by GC/MS analysis, including (S,E)-nerolidol (52.5%), τ-cadinol (21.6%) and S-falcarinol (3.6%). Accordi...

Direct supercriticalfluid extraction (SFE) of wines with carbon dioxide was compared to SFE of the sorbent used for solid-phase extraction of the same wine samples (SPE-SFE). Compared to SPE-SFE, the direct SFE results in amore specific and representative gas chromatographic fingerprint of the wine sample. The multivariate statistical processing of the direct SFE-GC data provides a clear-cut and sharp discrimination among the individual wine varieties while the discrimination based on the SPE-SFE-GC data is relatively poor. This finding reflects the adverse effects of additional analyte-sorbent interactions and sorption/desorption steps involved in SPE-SFE.

In the supercritical CO2-water-mineral systems relevant to subsurface CO2 sequestration, interfacial processes at the supercriticalfluid-mineral interface will strongly affect core- and reservoir-scale hydrologic properties. Experimental and theoretical studies have shown that water films will form on mineral surfaces in supercritical CO2, but will be thinner than those that form in vadose zone environments at any given matric potential. The theoretical model presented here allows assessment of water saturation as a function of matric potential, a critical step for evaluating relative permeabilities the CO2 sequestration environment. The experimental water adsorption studies, using Quartz Crystal Microbalance and Fourier Transform Infrared Spectroscopy methods, confirm the major conclusions of the adsorption/condensation model. Additional data provided by the FTIR study is that CO2 intercalation into clays, if it occurs, does not involve carbonate or bicarbonate formation, or significant restriction of CO2 mobility. We have shown that the water film that forms in supercritical CO2 is reactive with common rock-forming minerals, including albite, orthoclase, labradorite, and muscovite. The experimental data indicate that reactivity is a function of water film thickness; at an activity of water of 0.9, the greatest extent of reaction in scCO2 occurred in areas (step edges, surface pits) where capillary condensation thickened the water films. This suggests that dissolution/precipitation reactions may occur preferentially in small pores and pore throats, where it may have a disproportionately large effect on rock hydrologic properties. Finally, a theoretical model is presented here that describes the formation and movement of CO2 ganglia in porous media, allowing assessment of the effect of pore size and structural heterogeneity on capillary trapping efficiency. The model results also suggest possible engineering approaches for optimizing trapping capacity and for

A selective hydrogenation of maleic anhydride to either y-butyrolactone or succinic anhydride over simple Pd/Al(2)O(3) catalyst under supercritical CO(2) medium is described for the first time which has considerable promise for obht lab-scale as well as industrial selective hydro...

The specificity of supercriticalfluid,principle and schematic diagram of extraction are stated.The development in supercriticalfluid extraction the effective factor in plan such as plan essential oil(rose essential oil,seed oil from hippophae rhamnoides),plan pigment(capsicum pigment,tomato red pigment) and factors in Chinese medicine(astragaloside,artemisinini) are reviewed.And the development of supercriticalfluid extraction in future is forecasted.%文章论述了超临界流体的基本特性和萃取的原理,超临界流体在植物有效成分如植物精油、植物色素和中药有效成分等方面的研究现状,以及超临界流体萃取技术的发展趋势.

A new impetus for the development of electro physics is associated with using different types of electrical discharges in biology and medicine. These applications are based on their energetic and non-toxic factors affecting the medium on a cellular level. For the study of such processes, a mathematical model of a high-current low-temperature Z-discharge in a liquid, forming by the electrical explosion of a thin-walled metal shell, connected to a pulsed high-voltage generator, has been developed. High efficiency energy conversion, introduced into the plasma discharge to the energy of fluid motion, provides various bio chemical applications of such physical processes. The investigation is conducted through numerical solution of one-dimensional single-temperature non-stationary equations of radiation magneto hydrodynamics, one way describing the evolution of hydrodynamic, thermal and electrical characteristics of the medium throughout the area under consideration. The electrical approximation based on the assumption that the electric field in the discharge has a uniform distribution. The results are presented as a function of the electric current and the plasma channel length of time, as well as the temperature and pressure distributions at different time points along the radius of the cylindrical region in which the explosion occurs.

Full Text Available The synthesis of biodiesel fuel from lipids (vegetable oils and animal fats has gained in importance as a possible source of renewable non-fossil energy in an attempt to reduce our dependence on petroleum-based fuels. The catalytic processes commonly used for the production of biodiesel fuel present a series of limitations and drawbacks, among them the high energy consumption required for complex purification operations and undesirable side reactions. Supercriticalfluid (SCF technologies offer an interesting alternative to conventional processes for preparing biodiesel. This review highlights the advances, advantages, drawbacks and new tendencies involved in the use of supercriticalfluids (SCFs for biodiesel synthesis.

Full Text Available The formulations of washing cosmetics i.e. shower gels, containing extracts obtained during supercritical CO2 extraction process as active ingredient, were developed. The subject of the study was the analysis of the physicochemical and user properties of the obtained products. In the work supercritical CO2 extracts of black currant seeds, strawberry seeds, hop cones and mint leafs were used. The formulation contains a mixture of surfactants (disodium cocoamphodiacetate, disodium laureth sulfosuccinate, cocoamide DEA, cocoamidepropyl betaine, Sodium Laureth Sulfate. Various thickener agents were applied to the obtained desired rheological properties of the cosmetics. Among others, sorbitol acetal derivatives, methylhydroxypropylcellulose and C10-30 alkyl acrylate crosspolymer were used. For stable products, the effect of extracts addition (black currants seeds, strawberries seeds, mint and hops, obtained from supercritical CO2 extraction process on the cosmetics properties, such as pH, viscosity, detergency and foam ability, were determined. The obtained results showed that the extracts could be used as components of shower gels.

In this work, the SFE was applied to extract selected medicinal substances from sea buckthorn (Hippophae rhamnoides L.) leaves at different conditions (pressure 20-28 MPa, temperature 40-60 °C and ethanol concentration in CO2 0-6.9 wt. %) influencing solvent power of CO2. Interest was focused on the leaf oleoresin (total extract) and its minor components (fat soluble vitamins and carotenoids). The yield of polar component was still steadily increasing at the moment when the extraction is al...

A supercriticalfluid extraction (SFE) method with an online solid collection trap has been developed for the quantitative analysis of 16 polycyclic aromatic hydrocarbons (PAHs) and 15 typical PAH derivatives in solid matrix. Compared with liquid trapping and C18 solid-phase trapping, multi-walled carbon nanotubes (CNTs) were proved to be the most efficient trapping sorbent for the collection of PAHs and their nitro-, oxy- and alkyl-derivatives. The proposed extraction-collection procedure was systematically optimized in terms of pressure, temperature, extraction time, trapping materials, supercriticalfluid flow rate, co-solvent type, and co-solvent percentage, taking into account the interaction between these variables. The whole extraction process could be completed in 15min followed by GC-MS analysis. Quantitative recoveries of PAHs and their derivatives from spiked soil samples (50ngg(-1)) were obtained in the range of 62.9-111.8% with the precisions (RSD, intra-day) ranged from 1.9% to 13.7%. The developed SFE method with online CNTs trapping followed by GC-MS analysis has been demonstrated to be an efficient way for quantitative analysis of trace-level PAHs and their nitro-, oxy-, and alkyl-derivatives in soil samples.

Full Text Available In the field of drug delivery, the ability to control the size, morphology, and release of drug particles is fundamental to good targeting, but is often hampered by harsh processing conditions or inadequate methods; likewise for the processing of polymeric controlled-release systems. However, the use of supercriticalfluids such as supercritical CO2 (scCO2 has provided a ‘clean’ and effective alternative to traditional methods of drug and polymer processing. In particular, scCO2 has a number of unique properties that make it possible to process both bioactive molecules and amorphous polymers without using toxic organic solvents or elevated temperatures. Here, we review the positive impact that supercriticalfluids have had on the micronization, encapsulation, and impregnation of molecules of interest to both the pharmaceutical and biotechnology industries.